US 20100113717A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0113717 A1 Voskoboynikov et al. (43) Pub. Date: May 6, 2010

(54) PROCESS FOR PRODUCING SUBSTITUTED Publication Classification METALLOCENE COMPOUNDS FOR OLEFIN POLYMERIZATION (51) Int. Cl. CSF 4/6 (2006.01) (76) Inventors: Alexander Z. Voskoboynikov, C07F 1700 (2006.01) Moscow (RU); Alexey N. Ryabov, BOI 3L/2 (2006.01) Moscow (RU); Catalina L. Coker, BOI 3/4 (2006.01) Baytown, TX (US); Jo Ann M. (52) U.S. Cl...... 526/126; 556/11: 502/152: 502/117; Canich, Houston, TX (US) 556/53; 549/3: 502/155; 526/154 Correspondence Address: ExxonMobil Chemical Company (57) ABSTRACT Law Technology P.O. Box 21.49 Baytown, TX 77522-2149 (US) A process for producing a Substituted metallocene compound comprises reacting a first compound with a transfer-agent, (21) Appl. No.: 12/641,123 wherein the first compound comprises a complex of a transi tion metal atom selected from Group 3, 4, 5 or 6 of the (22) Filed: Dec. 17, 2009 Periodic Table of Elements, or a lanthanide metal atom, or actinide metal atom and at least one monocyclic or polycyclic Related U.S. Application Data ligand that is pi-bonded to M and is substituted with at least one halogen or Sulfonate Substituent and the transfer-agent (62) Division of application No. 1 1/302,997, filed on Dec. comprises a hydrocarbyl, Substituted hydrocarbyl, halocar 14, 2005. byl, substituted halocarbyl, silylcarbyl, or germylcarbyl radi (60) Provisional application No. 60/636,662, filed on Dec. cal capable of replacing said at least one halogen or Sulfonate 16, 2004. Substituent of said first compound under reaction conditions. US 2010/01 13717 A1 May 6, 2010

PROCESS FOR PRODUCING SUBSTITUTED synthesis or modification, and, then, metallocene preparation METALLOCENE COMPOUNDS FOR OLEFIN starting from each ligand synthesized. POLYMERIZATION 0008 For example, U.S. Pat. No. 5,840,644 describes cer tain metallocenes containing aryl-substituted indenyl deriva CROSS REFERENCE TO RELATED tives as ligands, which are said to provide propylene polymers APPLICATIONS having high isotacticity, narrow molecular weight distribu tion and very high molecular weight. However, synthesis of 0001. This application is a divisional of U.S. Ser. No. these compounds involves initial assembly of each aryl-Sub 11/302,997, filed Dec. 12, 2005 which claims priority from stituted indene ligand from a Substituted diphenyl compound U.S. Provisional Patent Application No. 60/636,662, filed on and then reaction of the ligand with MC1. Thus Example A Dec. 16, 2004. discloses synthesis of rac-dimethylsilylbis(2-methyl-4-phe nyl-indenyl)Zirconium dichloride by reaction of 2-phenyl FIELD benzyl bromide with diethylmethyl malonate and then KOH to produce 2-(2-phenylbenzyl)propionic acid, followed by 0002 This invention relates to a process for producing cyclization of the 2-(2-phenylbenzyl)propionic acid to pro Substituted metallocene compounds for use in olefin poly duce 2-methyl-4-phenylindan-1-one and reduction of the merization and to a process to polymerize olefins using Such 2-methyl-4-phenylindan-1-one to produce 2-methyl-7-phe Substituted metallocene compounds. nylindene. The 2-methyl-7-phenylindene is then reacted with dimethyldichlorosilane to produce dimethylbis(2-methyl-4- BACKGROUND phenylindenyl)silane, which is then reacted with butyllithium and zirconium tetrachloride to produce the desired bridged 0003 Various processes and catalysts exist for the metallocene. homopolymerization or copolymerization of olefins. For 0009. According to the present invention, a novel method many applications, it is desirable for a polyolefin to have a of producing Substituted metallocene complexes of early high weight average molecular weight while having a rela transition metals has been developed in which halogen Sub tively narrow molecular weight distribution. A high weight stituents on existing metallocene compounds are directly average molecular weight, when accompanied by a narrow replaced with other groups, such as hydrocarbyl groups. In molecular weight distribution, typically provides a polyolefin this way, a single base synthesis of a given halogen-substi with high strength properties. tuted metallocene compound can be used to generate a large 0004 Traditional Ziegler-Natta catalysts systems com number of final metallocene products with varying ligand prise a transition metal compound co-catalyzed by an alumi substituents. num alkyl and are typically capable of producing polyolefins 0010 Modification of the coordinated ligands of late tran having a high molecular weight, but with a broad molecular sition complexes, particularly, ferrocene derivatives, has been weight distribution. described (see Hassan, J.; Sevignon, M. Gozzi, C.; Schulz, 0005 More recently metallocene catalyst systems have E.; Lemaire, M. Chem. Rev. 2002, 102, 1359, and references been developed wherein the transition metal compound has therein). However, no similar transformations of early tran one or more cyclopentadienyl, indenyl or fluorenyl ring sition metal complexes, which include highly polarized and ligands (typically two). Metallocene catalyst systems, when reactive metal-ligand bonds, have been described so far. 0011 Scarce examples of transformations of the coordi activated with cocatalysts, such as alumoxane, are effective to nated cyclopentadienyl ligands of Group 4 metal complexes polymerize monomers to polyolefins having not only a high resulting in no modification of the nearest coordination poly weight average molecular weight but also a narrow molecular hedron have been described, e.g. H/D exchange in m-cyclo weight distribution. pentadienyls (Larsonneur, A.-M.; Choukroun, R., Jaud, J. 0006 Certain metallocenes containing substituted, Organometallics 1993, 12, 3216); Pd/C or PtC), catalyzed bridged indenyl derivatives are noted for their ability to pro hydrogenation of m-indenyls giving m-tetrahydroindenyls duce isotactic propylene polymers having high isotacticity (Wild, F. R. W. P. Zsolnai, L.; Huttner, G.; Brintzinger, H. H. and narrow molecular weight distribution. Considerable J. Organomet. Chem. 1982. 232, 233. Schäfer, A.; Karl, E.; effort has been made towards obtaining metallocene-pro Zsolani, L.; Huttner, G.; Brintzinger, H. H. J. Organomet. duced propylene polymers having ever-higher molecular Chem. 1987,328,87. Bandy, J. A.; Green, M. L. H.; Gardiner, weight and melting point, while maintaining Suitable catalyst I. M.; Prout, K. J. Chem. Soc., Dalton Trans. 1991, 2207. activity. Researchers currently theorize that there is a direct Rheingold, A. L.; Robinson, N. P.; Whelan, J.; Bosnich, B. relationship between the way in which a metallocene is sub Organometallics 1992, 11, 1869. Hollis, T. K.; Rheingold, A. stituted, and the molecular structure of the resulting polymer. L.; Robinson, N. P.; Whelan, J.; Bosnich, B. Organometallics For the substituted, bridged indenyl type metallocenes, it is 1992, 11, 2812); hydroboration of allyl- and vinyl-m-cyclo believed that the type and arrangement of substituents on the pentadienyl complexes (Erker, G.; Nolfe, R.; Aul, R.; Wilker, indenyl groups, as well as the type of bridge connecting the S.: Kriger, C.; Noe, R. J. Am. Chem. Soc. 1991, 113, 7594. indenyl groups, determines such polymer attributes as Erker, G.; Aul, R. Chem. Ber: 1991, 124, 1301); intramolecu molecular weight and melting point. lar photochemical 2+2 cycloaddition of vinyl-m-cyclopen 0007. There is, therefore, significant interest in producing tadienyl complexes (Erker, G.; Wilker, S.; Kriger, C.; Nolte, metallocene compounds with a variety of Substituents on the M. Organometallics 1993, 12, 2140); Ru-catalyzed metathe arenyl ligands. However, current methods for producing Sub sis of bis(allyl-m-cyclopentadienyl)Zirconium and -hafnium stituted metallocene compounds, and especially Group 4 dichlorides (Ogasawara, M.; Nagano, T.; Hayashi, T. J. Am. metallocene compounds, involve synthesis of each individual Chem. Soc. 2002, 124,9068). ligand family and then reaction with a simple metal deriva tive, such as MC1 and M(N(CH)), where M-Ti, Zr, or Hf, SUMMARY using transmetallation and amine elimination reactions, 0012. In one aspect, the invention resides in a process respectively. This methodology requires preliminary ligand producing a Substituted transition metal compound, the pro US 2010/01 13717 A1 May 6, 2010 cess comprising contacting: (a) a transition metal compound ated, linear or branched alicyclic hydrocarbyl substituent; or comprising at least one ligand having a halogen or Sulfonate a C-Coo Substituted or unsubstituted Saturated hydrocarbyl substituent directly bonded to any sp carbonatomat a bond radical; able ring position of said ligand, with (b), a transfer-agent t is the coordination number of the heteroatom T where “t-1- capable of replacing the halogen or Sulfonate Substituent of y’ indicates the number of R" substituents bonded to T; and the ligand with a hydrocarbyl, substituted hydrocarbyl, halo each X is, independently, a univalent anionic ligand, or two X carbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl are joined and bound to the metal atom to form a metallocycle Substituent, and (c) a coupling-catalyst. ring, or two X are joined to form a chelating ligand, a diene 0013. In a further aspect, the invention resides in a process ligand, or an alkylidene ligand; producing a substituted metallocene compound, the process provided that Z is substituted with at least one halogen or comprising: sulfonate substituent directly bonded to any sp carbon atom (a) providing a first compound represented by the formula (1): at a bondable ring position of the ligand Z, or that R" is substituted with at least one halogen or sulfonate substituent AMX, bonded to an sp carbon atom, or both. wherein: (b) reacting said first compound with a transfer-agent which M is a transition metal atom having a coordination number of comprises a hydrocarbyl, Substituted hydrocarbyl, halocar n (typically 2, 3, 4, 5, or 6) selected from Group 3, 4, 5 or 6 of byl, substituted halocarbyl, silylcarbyl, germylcarbyl radical the Periodic Table of Elements, or a lanthanide metal atom, or capable of replacing said at least one halogen or Sulfonate actinide metal atom, preferably a Group 4 transition metal Substituent of said first compound under reaction conditions, atom selected from titanium, Zirconium or hafnium; and in the presence of a coupling-catalyst. A is a monocyclic or polycyclic ligand that is pi-bonded to M 0015. In a preferred embodiment, Z is a substituted mono and is Substituted with at least one halogen or Sulfonate Sub cyclic or polycyclic arenyl ligand. In other embodiments, Z stituent directly bonded to any sp carbonatomat a bondable may include one or more ring heteroatoms selected from ring position of the ligand; and boron, a Group 14 atom that is not carbon, a Group 15 atom, each X is, independently, a univalent anionic ligand, or two X and a Group 16 atom. For example, Z can be a substituted are joined and bound to the metal atom to form a metallocycle cyclopentadienyl or heterocyclopentadienyl ligand, a Substi ring, or two X are joined to form a chelating ligand, a diene tuted indenyl or heteroindenyl ligand, or a substituted fluo ligand, or an alkylidene ligand; and renyl or heterofluorenyl ligand, or a substituted cyclopen (b) reacting said first compound with a transfer-agent which tanaphthyl or heterocyclopentanaphthyl ligand. comprises a hydrocarbyl, substituted hydrocarbyl, halocar 0016. In yet a further aspect, the invention resides in a byl, substituted halocarbyl, silylcarbyl, or germylcarbyl radi process for producing a Substituted metallocene compound, cal capable of replacing said at least one halogen or Sulfonate the process comprising: Substituent of said first compound under reaction conditions, (a) providing a first compound represented by the formula (2): and in the presence of a coupling-catalyst. 0014. In a further aspect, the invention resides in a process for producing a substituted metallocene compound, the pro cess comprising: (a) providing a first compound represented by the formula (3):

Z X wherein MN / M M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanide Q. M. N. metal atom, or actinide metal atom, preferably a Group 4 transition metal atom selected from titanium, Zirconium or hafnium; each of J and E is independently a substituted or unsubsti tuted, monocyclic or polycyclic ligand pi-bonded to M, wherein wherein at least one of Jand E includes at least one halogen or M is a Group 3, 4, 5 or 6 transition metal atom, or a lanthanide sulfonate substituent directly bonded to an sp carbonatomat metal atom, or actinide metal atom, preferably a Group 4 a bondable ring position of the ligand; transition metal atom selected from titanium, Zirconium or Q is an optional bridging group that is bonded to E and J. and hafnium; is present when y is one and absent wheny is Zero; Z is a Substituted or unsubstituted, monocyclic or polycyclic y is Zero or one; and ligand that is pi-bonded to M: each X is, independently, a univalent anionic ligand, or two X Q' is an optional bridging group that is bonded to Zand T, and are joined and bound to the metal atom to form a metallocycle is present when y is one and absent wheny is Zero; ring, or two X are joined to form a chelating ligand, a diene y is Zero or one; and ligand, or an alkylidene ligand; and T is a heteroatom with a coordination number of three from (b) reacting said first compound with a transfer-agent which Group 15 or with a coordination number of two from Group comprises a hydrocarbyl, Substituted hydrocarbyl, halocar 16 of the Periodic Table of Elements, and preferably is nitro byl, substituted halocarbyl, silylcarbyl, germylcarbyl radical gen, capable of replacing said at least one halogen or Sulfonate R" is selected from a C-Coo substituted or unsubstituted Substituent of said first compound under reaction conditions, monocyclic or polycyclic ring structure Substituent that is and in the presence of a coupling-catalyst. partially unsaturated, unsaturated or aromatic; or a C-Coo 0017. In a preferred embodiment, each of J and E may be Substituted or unsubstituted, unsaturated or partially unsatur independently selected from a substituted or unsubstituted US 2010/01 13717 A1

cyclopentadienyl ligand, a Substituted or unsubstituted het erocyclopentadienyl ligand, a Substituted or unsubstituted indenyl ligand, a Substituted or unsubstituted heteroindenyl ligand, or a substituted or unsubstituted fluorenyl ligand, a where R* is independently a hydrocarbyl or halocarbyl radi substituted or unsubstituted heterofluorenyl ligand, and a sub cal provided that at least one halogen atom remains on the stituted or unsubstituted cyclopentanaphthyl or a substituted original halocarbyl radical. Additionally, two or more R* may or unsubstituted heterocyclopentanaphthyl ligand. In another join together to form a Substituted or unsubstituted Saturated, embodiment, at least one of J and E includes one or more ring partially unsaturated or aromatic cyclic or polycyclic ring heteroatoms selected from boron, a Group 14 atom that is not Structure. carbon, a Group 15 atom, and a Group 16 atom. For example, 0026. Sillylcarbyl radicals (also called silylcarbyls) are 0018 Preferably, the halogen or sulfonate substituent groups in which the silyl functionality is bonded directly to bonded to J or E is a chloro, bromo, iodo, tosylate or triflate the indicated atom or atoms. Examples include SiH, SiHR*, substituent, and preferably is a chloro or bromo substituent. SiHR*, SiR*, SiH(OR*), SiH(OR*), Si(OR*) SiH, 0019. In a preferred embodiment, M is a Group 4 transi (NR*), SiH(NR*), Si(NR*), and the like where R* is tion metal atom selected from titanium, Zirconium and independently a hydrocarbyl or halocarbyl radical and two or hafnium. In a preferred embodiment the transfer agent is an more R* may join together to form a substituted or unsubsti organometallic compound, for example an organozinc com tuted Saturated, partially unsaturated or aromatic cyclic or pound or an organic compound of an alkali metal. In still a polycyclic ring structure. further aspect, the invention relates to a substituted metal 0027 Germylcarbyl radicals (also called germylcarbyls) locene compound produced by the process described herein are groups in which the germyl functionality is bonded and the use of the substituted metallocene compound in olefin directly to the indicated atom or atoms. Examples include polymerization catalyst systems and methods. GeH, GeHR*, GeHR*, GeR*, GeH(OR*), GeH(OR*), Ge(OR*), GeH(NR*), GeH(NR*), Ge(NR*), and the DEFINITIONS like where R* is independently a hydrocarbyl or halocarbyl 0020. As used herein, the numbering scheme for the Peri radical and two or more R* may join together to form a odic Table Groups is the new notation as set out in CHEMICAL Substituted or unsubstituted Saturated, partially unsaturated AND ENGINEERING NEWS, 63(5), 27 (1985). or aromatic cyclic or polycyclic ring structure. 0021. As used herein, is methyl, Et is ethyl, t-Bu and Bu 0028 Polar radicals, functional groups or polar groups are are tertiary butyl, iPrand Prare isopropyl, Cy is cyclohexyl, groups in which a heteroatom functionality is bonded directly THF (also thf) is tetrahydrofuran, Phis phenyl, Tf is triflate, to the indicated atom or atoms. They include heteroatoms of and TS is tosylate. Groups 1-17 of the periodic table either alone or connected to 0022. The terms “hydrocarbyl radical,”“hydrocarbyland other elements by covalent or other interactions such as ionic, "hydrocarbyl group' are used interchangeably throughout Van der Waals forces, or hydrogen bonding. Examples of this document. Likewise the terms “group”, “radical, and functional groups include carboxylic acid, acid halide, car “substituent are also used interchangeably in this document. boxylic ester, carboxylic salt, carboxylic anhydride, aldehyde For purposes of this disclosure, “hydrocarbyl radical is and their chalcogen (Group 14) analogues, alcohol and phe defined to be a radical, which contains hydrogenatoms and up nol, ether, peroxide and hydroperoxide, carboxylic amide, to 100 carbon atoms and which may be linear, branched, or hydrazide and imide, amidine and other nitrogen analogues of cyclic, and when cyclic, may be aromatic or non-aromatic. amides, nitrile, amine and imine, azo, nitro, other nitrogen 0023 Substituted hydrocarbyl radicals are radicals in compounds, Sulfur acids, selenium acids, thiols, sulfides, Sul which at least one hydrogenatom has been substituted with at foxides, Sulfones, Sulfonates, phosphines, phosphates, other least one functional group such as NR*, OR*, SeR*, TeR*, phosphorus compounds, silanes, boranes, borates, alanes, PR* AsR*, SbR*, SR*, BR*, SiR*, GeR*. SnR*, aluminates. Functional groups may also be taken broadly to PbR* and the like or where at least one non-hydrocarbon include organic polymer Supports or inorganic Support mate atom or group has been inserted within the hydrocarbyl radi rial Such as alumina, and silica. Preferred examples of polar groups include NR*, OR*, SeR*, TeR*, PR*, AsR*, SbR*, SR*, BR*, SnR*, PbR*, and the like where R* is independently a hydrocarbyl, substituted hydrocarbyl, halo (R*) - Sn(R*) -, -Pb(R*) - and the like, where R* carbyl or substituted halocarbyl radical as defined above and is independently a hydrocarbylor halocarbyl radical, and two two R* may join together to form a substituted or unsubsti or more R* may join together to form a substituted or unsub tuted Saturated, partially unsaturated or aromatic cyclic or stituted Saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. Also preferred are Sulfonate radi polycyclic ring structure. cals, S(=O),OR*, where R* is independently a hydrocarbyl, 0024 Halocarbyl radicals are radicals in which one or substituted hydrocarbyl, halocarbyl or substituted halocarbyl more hydrocarbyl hydrogenatoms have been substituted with radical as defined above and two R* may join together to form at least one halogen (e.g. F. Cl, Br, I) or halogen-containing a Substituted or unsubstituted Saturated, partially unsaturated group (e.g. CFs). or aromatic cyclic or polycyclic ring structure. Examples 0025. Substituted halocarbyl radicals are radicals in which include SOMe (mesylate), SO(4-tosyl) (tosylate), SOCF at least one halocarbyl hydrogen or halogen atom has been (triflate), SO(n-CF) (nonaflate) and the like. substituted with at least one functional group such as NR*, 0029. In using the terms “substituted or unsubstituted OR*, SeR*, TeR*, PR* AsR*, SbR*, SR*, BR*, SiR*, cyclopentadienyl ligand”, “substituted or unsubstituted het GeR*, SnR*, PbR* and the like or where at least one erocyclopentadienyl ligand”, “substituted or unsubstituted non-carbon atom or group has been inserted within the halo indenyl ligand”, “substituted or unsubstituted heteroindenyl carbyl radical Such as —O— —S— —Se—, —Te—, ligand”, “substituted or unsubstituted fluorenyl ligand”, “sub US 2010/01 13717 A1 May 6, 2010 stituted or unsubstituted heterofluorenyl ligand”, “substituted would include 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2.5- or unsubstituted cyclopentanaphthyl ligand”, “substituted or dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, unsubstituted heterocyclopentanaphthyl ligand”, “substi and 3,5-dimethylphenyl. tuted or unsubstituted heterocyclopenta-pentayl ligand. 0031. For nomenclature purposes, the following number “substituted or unsubstituted heterophenyl ligand”, “substi ing schemes are used for cyclopentadienyl, indenyl, fluorenyl tuted or unsubstituted heteropentalenyl ligand”, “substituted and cyclopentanaphthyl (also termed benzindenyl). It should or unsubstituted heterocyclopentapentalenyl ligand”, “sub be noted that indenyl can be considered as cyclopentadienyl stituted or unsubstituted heterocyclopentaindenyl ligand. with a fused benzene ring. Analogously, fluorenyl can be “substituted or unsubstituted heterobenzocyclopentaindenyl considered as indenyl with a benzene ring fused to the five ligand”, “substituted or unsubstituted pentalenyl ligand', membered ring on the indenyl. Each structure below is drawn “substituted or unsubstituted monocyclic ligand”, “substi and named as an anion. tuted or unsubstituted monocyclic arenyl ligand”, “substi 4 3 4 3 tuted or unsubstituted polycyclic ligand’, or “substituted or unsubstituted polycyclic arenyl ligand’, the Substitution to the aforementioned ligand is on a bondable ring position, and 5 (O) 2 6 O) 2 OO)7 each occurrence is selected from hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, cyclopentadienyl indenyl germylcarbyl, a halogen radical, or a polar group. 6 5 4 3 5 4 3 0030. In some embodiments, the hydrocarbyl radical is 6 independently selected from methyl, ethyl, ethenyl and iso 7 2 2 mers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, 7 decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl 8 9 8 9 hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hene fluorenyl cyclopentabnaphthyl icosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, 5 4 heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, bute nyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, 6 undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadece nyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, 7 (O) O 32 eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, 8 9 pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nona cosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl, cyclopentaanaphthyl heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, hepta 0032. A similar numbering and nomenclature scheme is decynyl, octadecynyl. nonadecynyl, eicosynyl, heneicosynyl, used for heterocyclopentadienyls, heterophenyls, heteropen docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosy talenyls, heterocyclopentapentalenyls, heteroindenyls, heter nyl, heptacosynyl, octacosynyl. nonacosynyl, triacontynyl, ofluorenyls, heterocyclopentanaphthyls, heterocyclopentain butadienyl, pentadienyl, hexadienyl, heptadienyl, octadienyl, denyls, heterobenzocyclopentaindenyls, and the like, as nonadienyl, and decadienyl. Also included are isomers of illustrated below. Each structure is drawn and named as an saturated, partially unsaturated and aromatic cyclic and poly anion. cyclic structures wherein the radical may additionally be 0033 Non-limiting examples of heterocyclopentadienyls subjected to the types of substitutions described above. include: Examples include phenyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl, 4 3 3 benzyl, methylbenzyl, naphthyl, anthracenyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, cycloheptyl, cycloheptenyl, norbornyl, norbornenyl, ada O-os,2 O-os, O-os, manty1 and the like. For this disclosure, when a radical is 3-dimethylamino 1,3-azaborollide 2-dimethylamino 2-dimethylamino listed, it indicates that radical type and all other radicals 1,2-oxaborollide 1,2-thia borollide formed when that radical type is subjected to the substitutions defined above. Alkyl, alkenyl and alkynyl radicals listed include all isomers including where appropriate cyclic iso mers, for example, butyl includes n-butyl, 2-methylpropyl. O. O. 1-methylpropyl, tent-butyl, and cyclobutyl (and analogous Substituted cyclopropyls); pentyl includes n-pentyl, cyclo aZacyclopentadienyl phosphacyclopentadienyl pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-eth 3 3 ylpropyl, and neopentyl (and analogous Substituted cyclobu tyls and cyclopropyls); butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-prop enyl, 1-me O. O. O. thyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-pro arsacyclopentadienyl stibacyclopentadienyl boracyclopentadienyl penyl (and cyclobutenyls and cyclopropenyls). Cyclic com pound having Substitutions include all isomer forms, for example, methylphenyl would include ortho-methylphenyl, 0034) Further non-limiting examples of heterocyclopenta meta-methylphenyl and para-methylphenyl; dimethylphenyl dienyls include 1,3-diazacyclopentadienyl, 1.3-diphosphacy US 2010/01 13717 A1 May 6, 2010 clopentadienyl, 1,3-diarsacyclopentadienyl, 1.3-distibacy clopentadienyl, 1,3-diboracyclopentadienyl, 1,3- -continued aZaphosphacyclopentadienyl, 1.3-azaarsacylcopentadienyl, 3 4 3 4 3 4 1.3-aZaStibacyclopentadienyl, 1.3-azaboracyclopentadienyl, 1.3-arsaphosphacyclopentadienyl, 1.3-arsastibacyclopenta dienyl, 1.3-arsaboracyclopentadienyl, 1,3-boraphosphacy (OO)S 6 (OO)6 (OO)O 6 clopentadienyl, 1.3-borastibacylcopentadienyl, 1.3-phos cyclopentabthienyl cyclopentacthienyl cyclopentablfuryl phastibacyclopentadienyl, 1,2-diazacyclopentadienyl, 1.2- 3 4 diphosphacyclopentadienyl, 1.2-diarsacyclopentadienyl, 3 4 1.2-distibacyclopentadienyl, 1,2-diboracyclopentadienyl, 2 OO). 2COO) P 1.2-aZaphosphacyclopentadienyl, 1,2-azaarsacylcopentadi 6 6 / enyl, 1,2-azastibacyclopentadienyl, 1,2-azaboracyclopenta Me dienyl, 1,2-arsaphosphacyclopentadienyl, 1.2-arsastibacy cyclopentacfuryl 1-methylcyclopentabphospholyl clopentadienyl, 1.2-arsaboracyclopentadienyl, 1.2- boraphosphacyclopentadienyl, 1.2- borastibacylcopentadienyl, 1.2- phosphastibacyclopentadienyl, 3-dihydrocarbylamino-1,3- azaborollide, 2-dihydrocarbylamino-1,2-oxaborollide, 2-dihydrocarbylamino-1,2-thiaborollide, 3-hydrocarbyloxy 2-methylcyclopentacphospholyl 1,3-azaborollide, 2-hydrocarbyloxy-1,2-oxaborollide, 2-hy drocarbyloxy-1,2-thiaborollide, 3-hydrocarbyl-1,3- 0038. Further non-limiting examples of heteropentalenyls azaborollide, 2-hydrocarbyl-1,2-oxaborollide, and include cyclopentablselenophenyl, cyclopentacSelenophe 2-hydrocarbyl-1,2-thiaborollide, where hydrocarbyl is a nyl, cyclopentabtellurophenyl, cyclopentactellurophenyl, “hydrocarbyl radical as previously defined. 1-hydrocarbylcyclopentabarsolyl, 2-hydrocarbylcyclo 0035 Non-limiting examples of heterophenyls include: pentacarsolyl, 1-hydrocarbylcyclopentabstibolyl, 2-hy drocarbylcyclopentacistibolyl, 1-hydrocarbylcyclopentab 3 2 6 5 pyrrolyl, 2-hydrocarbylcyclopentacpyrrolyl, M M 4 1-hydrocarbylcyclopentablphospholyl, and 2-hydrocarbyl 4 -NMe 1 P B-NMe cyclopentacphospholyl, where hydrocarbyl is a “hydrocar

5 6 2 3 byl radical as previously defined. 1-dimethylamino 4-dimethylamino 0039. Non-limiting examples of heterocylopentapental boratabenzene 1,4-phosphaboratabenzene enyls include the following, where Z" and Q" independently represent the heteroatoms O, S, Se, or Te, or heteroatom groups, NR**, PR**, AsR**, or SbR** where R** is hydro 5 O/ B-NM 2 gen, or a hydrocarbyl, Substituted hydrocarbyl, halocarbyl, S substituted halocarbyl, silylcarbyl, or germylcarbyl substitu 1-dimethylamino ent. boratabenzene

0036 Further non-limiting examples of heterophenyls include 1-dihydrocarbylaminoboratabenzene, 4-dihydrocar bylamino-1,4-phosphaboratabenzene, 2-dihydrocarby lamino-1,2-azaboratabenzene, 1-hydrocarbyloxyborataben Zene, 4-hydrocarbyloxy-1,4-phosphaboratabenzene, 2-hydrocarbyloxy-1,2-azaboratabenzene, 1-hydrocarbylbo ratabenzene, 4-hydrocarbyl-1,4-phosphaboratabenzene, and 2-hydrocarbyl-1,2-azaboratabenzene, where hydrocarbyl is a “hydrocarbyl radical as previously defined. 0037 Non-limiting examples of heteropentalenyls include:

3 4

Me 1-methylcyclopentablpyrrolyl 2-methylcyclmethylcyclopentacpyrroly t lwl US 2010/01 13717 A1 May 6, 2010

0044) Further non-limiting examples of heterocyclopen -continued tanaphthyls include cyclopentaglphosphinolyl, cyclopenta 3 Z glisophosphinolyl, cyclopentaglarsinolyl, and cyclopenta 6 5 glisoarsinolyl. O Q.it 0045. Non-limiting examples of heterocyclopentainde 7 nyls include:

0040. Non-limiting examples of heteroindenyls include: 3 4 5 2 4 3 NMs 4 3 MešOC DO) 8 7 5 B 5 O B-NMe2 2-methylcyclopentafisoindolyl 6 O) . S ve S 7 3 4 5 3 4 5 2-dimethylamino-1,2- 3-dimethylamino-1,3- benzothia borollide benzothia borollide 4 3 4 5 4 5 Q 8 7 s 8 7 5 N 3 3 indeno.5,6-bifuryl indeno.5,6-bithienyl 6 BO) 2 ( )O) N( )O) 3 4 5 3 4 5 7 N 7 7 3a,7a-azaborindenyl cyclopentablpyridyl cyclopentaclpyridyl 4 5 4 5 8 7 8 7 3 3 indeno.5,6-clfuryl indeno.5,6-cithienyl

P 2 P 7 7 cyclopentacphosphinyl cyclopentabphosphinyl

0041 Further non-limiting examples of heteroindenyls include cyclopentabarsinyl, cyclopentacarsinyl, cyclo pentabstibinyl, cyclopentacistibinyl, 3-dihydrocarby lamino-1,3-benzothiaborollide, 2-dihydrocarbylamino-1,2- benzothiaborollide, 3-hydrocarbyloxy-1,3- benzothiaborollide, 2-hydrocarbyloxy-1,2- benzothiaborollide, 3-hydrocarbyl-1,3-benzothiaborollide, and 2-hydrocarbyl-1,2-benzothiaborollide, where hydrocar byl is a “hydrocarbyl radical as previously defined. 0042. Non-limiting examples of heterofluorenyls include:

cyclopentab1benzothienyl indeno1,2-bithienyl e

5 indeno12-cpyridyl indeno12-cphosphinyl 6 0043. Non-limiting examples of heterocyclopentanaphth of O.8 7 yls include: indeno12-cithienyl 4-methylcyclopentablindolyl

0046. Further non-limiting examples of heterocyclopen taindenyls include 1-hydrocarbylcyclopentaflphosphin dolyl, 2-hydrocarbylcyclopentafisophosphindolyl, 1-hy OOOOOO drocarbylcyclopentafarsindolyl, 2-hydrocarbylcyclopenta cyclopentagduinolyl cyclopentagisoquinolyl fisoarsindolyl, indeno.5,6-biselenophenyl, indeno.5,6-b tellurophenyl, indeno.5,6-cselenophenyl, indeno.5,6-c tellurophenyl, 2-hydrocarbylcyclopentafisoindolyl, and US 2010/01 13717 A1 May 6, 2010

1-hydrocarbylcyclopenta findolyl, where hydrocarbyl is a “hydrocarbyl radical as previously defined. 0047. Non-limiting examples of heterobenzocyclopen taindenyls include: 7 )

"heteroatom substituent' "ring heteroatom"

0050. A “ring carbonatom' is a carbon atom that is part of a cyclic ring structure. By this definition, an indenyl fragment has nine ring carbon atoms. 0051. A “bondable ring position' is a ring position that is capable of bearing a Substituent or bridging Substituent. For example, cyclopentabthienyl has five bondable ring posi tions (at the carbon atoms) and one non-bondable ring posi tion (the sulfur atom): cyclopentablpyrrolyl has six bondable ring positions (at the carbon atoms and at the nitrogen atom). 5-methylindeno2,1-bindolyl 0.052 The term “arenyl ligand is used herein to mean an unsaturated cyclic hydrocarbylligand that can consist of one ring, or two or more fused or catenated rings. Cyclopentadi enyl ligands, indenyl ligands, and fluorenyl ligands are all examples of arenyl ligands. 0053 As used herein, the term “monocyclic ligand is Obs, intended to mean any substituted or unsubstituted Cs to Coo indeno1,2-b1benzothienyl monoanionic aromatic five-membered or six-membered single ring structure composed of ring carbon atoms, either alone or in combination with one or more ring heteroatoms. Further, the term “monocyclic arenyl ligand is used hereinto mean a substituted or unsubstituted monoanionic Cs to Coo hydrocarbylligand that contains an aromatic five-membered single hydrocarbyl ring structure (also referred to as a cyclo pentadienyl ring). indeno2,1-b1benzothienyl 0054 As used herein, the term “polycyclic ligand is intended to mean any Substituted or unsubstituted Cs to Co 0048. Further non-limiting examples of heterobenzocy monoanionic partially unsaturated or aromatic multiple fused clopentaindenyls include 5-hydrocarbylindeno1,2-bindolyl ring structure containing at least one aromatic five-membered and 5-hydrocarbylindeno.2.1-bindolyl, where hydrocarbyl ring structure, said ligand composed of ring carbon atoms, either alone or in combination with one or more ring heteroa is a “hydrocarbyl radical as previously defined. toms. Further, the term “polycyclic arenyl ligand is used 0049. A “ring heteroatom' is a heteroatom that is within a hereinto mean a Substituted or unsubstituted monoanionic Cs cyclic ring structure. A "heteroatom substituent” is a heteroa to Co. hydrocarbyl ligand that contains an aromatic five tom containing group that is directly bonded to a ring struc membered hydrocarbyl ring (also referred to as a cyclopen ture through the heteroatom. The terms “ring heteroatom’ tadienyl ring) that is fused to one or two partially unsaturated, and "heteroatom substituent” are illustrated below where Z." or aromatic hydrocarbyl ring structures which may be fused is a heteroatom group preferably S, O, Se, Te, N-R", P R", to additional saturated, partially unsaturated, or aromatic As R", Sb-R" or B-R" and each R" is independently hydrocarbyl rings. hydrogen or a hydrocarbyl, Substituted hydrocarbyl, halocar 0055 Monocyclic ligands include, but are not limited to, byl or substituted halocarbyl radical as defined above, and substituted or unsubstituted heterocyclopentadienyls, het two R" may join together to form a substituted or unsubsti erophenyls, and cyclopentadienyls. Monocyclic arenyl tuted Saturated, partially unsaturated or aromatic cyclic or ligands, include Substituted or unsubstituted cyclopentadi polycyclic ring structure. If R" is bonded to boron, R" can enyls. Polycyclic ligands include, but are not limited to, Sub additionally be a Group 15 or Group 16 group where the stituted or unsubstituted, partially unsaturated or aromatic heteroatom is directly bonded to boron and R" is then prefer heteroindenyls, heteropentalenyls, heterocyclopentapental ably an O-R" group or an N-R" group, where each R" enyls, heterofluorenyls, heterocyclopentanaphthyls, hetero is independently hydrogen or a hydrocarbyl, Substituted cyclopentaindenyls, heterobenzocyclopentaindenyls, inde hydrocarbyl, halocarbyl or substituted halocarbyl radical as nyls, pentalenyls, fluorenyls, and cyclopentanaphthyls. defined above and two R" may join together to form a sub Polycyclic arenyl ligands include, but are not limited to, sub stituted or unsubstituted Saturated, partially unsaturated or stituted or unsubstituted, partially unsaturated or aromatic aromatic cyclic or polycyclic ring structure. indenyls, pentalenyls, fluorenyls, and cyclopentanaphthyls. US 2010/01 13717 A1 May 6, 2010

0056. Non-limiting examples of polycyclic arenyl ligands, tridecamethyleneindenyl, 5,6-tetradecamethyleneindenyl, named as monoanionic ligands, include indenyl, 4.5-dihy 4.5-tetradecamethyleneindenyl, 5,6-pentadecamethylenein droindenyl, 4,7-dihydroindenyl, 4,5,6,7-tetrahydroindenyl, denyl, 4.5-pentadecamethyleneindenyl, 5.6-hexadecameth fluorenyl, 1,2-dihydrotetrahydrofluorenyl, 1,4-dihydrotet yleneindenyl, 4.5-hexadecamethyleneindenyl, 5.6-hepta rahydrofluorenyl, 3,4-dihydrotetrahydrofluorenyl, 1,2,3,4- decamethyleneindenyl, 4.5-heptadecamethyleneindenyl, tetrahydrofluorenyl, 1,2,5,6-tetrahydrofluorenyl, 1,2,7,8-tet 5,6-octadecamethyleneindenyl, 4.5-octadecamethyleneinde rahydrofluorenyl, 3,4,5,6-tetrahydrofluorenyl, 14.5.8- nyl, 5.6-nonadecamethyleneindenyl, 4.5-nonadecamethyl tetrahydrofluorenyl, 1,2,3,4,5,6,7,8-octahydrofluorenyl, eneindenyl, 5.6-eicosamethyleneindenyl, 4.5-eicosamethyl cyclopentabnaphthyl, 4.4a-dihydrocyclopentabnaphthyl, eneindenyl, (6Z.8Z.10Z)-cyclooctaeindenyl, (5Z,7Z.9Z)- cyclooctaflindenyl, (5E,7Z.9E, 11Z,13E)-cyclododecaf 5,6-dihydrocyclopentabnaphthyl, 5,8-dihydrocyclopenta indenyl, (6E.8Z.10E,12Z,14E)-cyclododecaeindenyl, benz Ibnaphthyl, 4,9-dihydrocyclopentabnaphthyl, 4.4a.5,6-tet afluorenyl, benzbfluorenyl, benzcifluorenyl, naphth 2,3- rahydrocyclopentabnaphthyl, 4.5.8.9-tetrahydrocyclopenta afluorenyl, naphth 2,3-bfluorenyl, naphth 2.3-c fluorenyl, Ibnaphthyl, 4.4a,7,8-tetrahydrocyclopentabnaphthyl, naphth 1,2-afluorenyl, naphth 1,2-bifluorenyl, naphth 1,2- 4.4a.8a,9-tetrahydrocyclopentabnaphthyl, 5,6,7,8-tetrahy cfluorenyl, 2,3-tetramethylenefluorenyl, 1,2-tetramethyl drocyclopentabnaphthyl, 4.4a.5,8-tetrahydrocyclopentab enefluorenyl, 3,4-tetramethylenefluorenyl, 2,3-trimethylene naphthyl, 4,5,6,9-tetrahydrocyclopentabnaphthyl, 4,6,7,8- fluorenyl, 1.2-trimethylenefluorenyl, 3,4-trimethylene fluo tetrahydrocyclopentabnaphthyl, 4,6,7,9- renyl, 2,3-pentamethylenefluorenyl, 1.2-pentamethylene tetrahydrocyclopentabnaphthyl, 4.4a.5.9- fluorenyl, 3,4-pentamethylenefluorenyl, 2.3-hexamethylene tetrahydrocyclopentabnaphthyl, 4.4a.5,6,7,8- fluorenyl, 1.2-hexamethylenefluorenyl, 3,4- hexahydrocyclopentabnaphthyl, 4,4a,5,6,8a,9- hexamethylenefluorenyl, 2.3-heptamethylene fluorenyl, 1.2- hexahydrocyclopentabnaphthyl, 4,4a,5,8,8a,9- heptamethylenefluorenyl, 3,4-heptamethylenefluorenyl, 2.3- hexahydrocyclopentabnaphthyl, 4,5,6,7,8,9- octamethylenefluorenyl, 1,2-octamethylene fluorenyl, 3,4- hexahydrocyclopentabnaphthyl, 4.4a.5,6,7,9- octamethylene fluorenyl, 2.3-nonamethylenefluorenyl, 1.2- hexahydrocyclopentabnaphthyl, 4.4a.5,6,7,8,8a,9- nonamethylenefluorenyl, 3.4-nonamethylenefluorenyl, 2.3- octahydrocyclopentabnaphthyl, cyclopentaanaphthyl, decamethylenefluorenyl, 1,2-decamethylenefluorenyl, 3,4- 4.5-dihydrocyclopentaanaphthyl, 6,7-dihydrocyclopenta decamethylenefluorenyl, 2.3-undecamethylenefluorenyl, anaphthyl, 8,9-dihydrocyclopentaanaphthyl, 5a,9a-dihy 1.2-undecamethylenefluorenyl, 3,4-undecamethylenefluore drocyclopentaanaphthyl, 6,9-dihydrocyclopentaanaph nyl, 2.3-dodec amethylenefluorenyl, 1,2-dodecamethylene thyl, 7.9a-dihydrocyclopentaanaphthyl, 4.9a fluorenyl, 3,4-dodecamethylenefluorenyl, 2,3-tetramethyl dihydrocyclopentaanaphthyl, 5a,8-dihydrocyclopentaa ene-6,7-tetramethylenefluorenyl, 1,2-tetramethylene-7,8- naphthyl, 4.5.5a,9a-tetrahydrocyclopentaanaphthyl, 4.5.6. tetramethylene fluorenyl, 3,4-tetramethylene-5,6- 7-tetrahydrocyclopentaanaphthyl, 4,5,8,9- tetramethylenefluorenyl, bis-benz2.3:6.7 fluorenyl, bis tetrahydrocyclopentaanaphthyl, 5a,6,7,9a benz2.3:5.6fluorenyl, bis-benz 1.2.7.8 fluorenyl, bis-benz tetrahydrocyclopentaanaphthyl, 6,7,8,9- 1.2:5,6fluorenyl, bis-benz 1.2:6.7fluorenyl, bis-benz 1.2: tetrahydrocyclopentaanaphthyl, 5a,8,9,9a 7.8 fluorenyl, and bis-benz3,4,5,6fluorenyl, tetrahydrocyclopentaanaphthyl, 4,5,7,9a tetrahydrocyclopentaanaphthyl, 5a,6,7,9a 0057 Partially hydrogenated polycyclic arene ligands tetrahydrocyclopentaanaphthyl, 7,8,9,9a retain the numbering scheme of the parent polycyclic arene tetrahydrocyclopentaanaphthyl, 4,6,7,9a ligand, namely the numbering schemes defined for indenyl, tetrahydrocyclopentaanaphthyl, 4,8,9,9a fluorenyl, cyclopentabnaphthyl, cyclopentaanaphthyl tetrahydrocyclopentaanaphthyl, 4,5,6,9- ligands. tetrahydrocyclopentaanaphthyl, 45.5a,8- 0058. In the context of this document, “homopolymeriza tetrahydrocyclopentaanaphthyl, 5a,6,7,8- tion” would produce a polymer made from one monomer. For tetrahydrocyclopentaanaphthyl, 5a,6,9.9a example, homopolymerization of propylene would produce tetrahydrocyclopentaanaphthyl, 5a,6,7,8,9,9a homopolypropylene. Homopolymerization of ethylene hexahydrocyclopentaanaphthyl, 4,6,7,8,9,9a would produce homopolyethylene. Likewise, "copolymer hexahydrocyclopentaanaphthyl, 4,5,7,8,9,9a ization” would produce polymers with more than one mono hexahydrocyclopentaanaphthyl, 4,5,5a,8,9,9a mer type. For example, ethylene copolymers include poly hexahydrocyclopentaanaphthyl, 45.5a,6,9.9a mers of ethylene with C-olefins, cyclic olefins and diolefins, hexahydrocyclopentaanaphthyl, 45.5a,6,7,9a vinylaromatic olefins, C.-olefinic diolefins, substituted C-ole hexahydrocyclopentaanaphthyl, 45.5a,6,7,8- fins, and/or acetylenically unsaturated monomers. hexahydrocyclopentaanaphthyl, 4,5,6,7,8,9- 0059 Non-limiting examples of C-olefins include ethyl hexahydrocyclopentaanaphthyl, 45.5a,6,7,8,9,9a ene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, hexahydrocyclopentaanaphthyl, 45.5a,6,7,8,9,9a 1-octene, 1-nonene, 1-decene, 1-undecene 1-dodecene, octahydrocyclopentaanaphthyl, 5,6-trimethyleneindenyl, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 4,5-trimethyleneindenyl, 5,6-pentamethyleneindenyl, 4.5- 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, pentamethyleneindenyl, 5,6-hexamethyleneindenyl, 4.5- 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, hexamethyleneindenyl, 5,6-heptamethyleneindenyl, 4.5- 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, heptamethyleneindenyl, 5,6-octamethyleneindenyl, 4.5- 1-nonacosene, 1-triacontene, 4-methyl-1-pentene, 3-methyl octamethyleneindenyl, 5,6-nonamethyleneindenyl, 4.5- 1-pentene, 5-methyl-1-nonene, 3.5.5-trimethyl-1-hexene, nonamethyleneindenyl, 5,6-decamethyleneindenyl, 4.5- vinylcyclohexane, and vinylnorbornane. decamethyleneindenyl, 5.6-undecamethyleneindenyl, 4.5- 0060. Non-limiting examples of cyclic olefins and diole undecamethyleneindenyl, 5,6-dodecamethyleneindenyl, 4.5- fins include cyclobutene, cyclopentene, cyclohexene, cyclo dodecamethyleneindenyl, 5,6-tridecamethyleneindenyl, 4.5- heptene, cyclooctene, cyclononene, cyclodecene, nor US 2010/01 13717 A1 May 6, 2010

bornene, 4-methylnorbornene, 2-methylcyclopentene, Such a pair after activation, it means the activated catalyst and 4-methylcyclopentene, vinylcyclohexane, norbornadiene, the activator or other charge-balancing moiety. dicyclopentadiene, 5-ethylidene-2-norbornene, vinylcyclo 0066. The transition metal compound may be neutral as in hexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane, 1.2- a precatalyst, or a charged species with a counterion as in an divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcy activated catalyst System. clohexane, 1.5-divinylcyclooctane, 1-allyl-4- 0067 Catalyst precursor is also often referred to as pre vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5- catalyst, catalyst, catalyst compound, catalyst precursor, tran vinylcyclooctane, and 1,5-diallylcyclooctane. sition metal compound or transition metal complex. These 0061 Non-limiting examples of vinylaromatic olefins words are used interchangeably. Activator and cocatalyst are include styrene, para-methylstyrene, para-t-butylstyrene, also used interchangeably. A Scavenger is a compound that is vinylnaphthylene, vinyltoluene, and divinylbenzene. typically added to facilitate oligomerization or polymeriza 0062. Non-limiting examples of C.-olefinic dienes include tion by Scavenging impurities. Some scavengers may also act 1,4-hexadiene, 1.5-hexadiene, 1.5-heptadiene, 1.6-heptadi as activators and may be referred to as co-activators. A co ene, 6-methyl-1,6-heptadiene, 1.7-octadiene, 7-methyl-1,7- activator, that is not a scavenger, may also be used in con octadiene, 1.9-decadiene, 1,11-dodecene, 1,13-tetradecene junction with an activator in order to form an active catalyst. and 9-methyl-1,9-decadiene. In some embodiments a co-activator can be pre-mixed with 0063 Substituted C-olefins (also called functional group the transition metal compound to forman alkylated transition containing C-olefins) include those containing at least one metal compound, also referred to as an alkylated invention non-carbon Group 13 to 17 atom bound to a carbon atom of compound. the substituted C-olefin where such substitution if silicon may 0068. Noncoordinating anion (NCA) is defined to mean an be adjacent to the double bond or terminal to the double bond, anion either that does not coordinate to the catalyst metal or anywhere in between, and where inclusion of non-carbon cation or that does coordinate to the metal cation, but only and non-silicon atoms such as for example B, O, S, Se, Te, N. weakly. An NCA coordinates weakly enough that a neutral P. Ge. Sn, Pb, AS, F, Cl, Br, or I, are contemplated, where such Lewis base. Such as an olefinically or acetylenically unsatur non-carbon or non-silicon moieties are sufficiently far ated monomer can displace it from the catalyst center. Any removed from the double bond so as not to interfere with the metal or metalloid that can form a compatible, weakly coor coordination polymerization reaction with the catalyst and so dinating complex may be used or contained in the noncoor to retain the generally hydrocarbyl characteristic. By suffi dinating anion. Suitable metals include, but are not limited to, ciently far removed from the double bond we intend that the aluminum, gold, and platinum. Suitable metalloids include, number of carbonatoms, or the number of carbon and silicon but are not limited to, boron, aluminum, phosphorus, and atoms, separating the double bond and the non-carbon or silicon. non-silicon moiety is preferably 6 or greater, e.g. 7, or 8, or 9. 0069. A stoichiometric activator can be either neutral or or 10, or 11, or 12, or 13, or 14 or more. The number of such ionic. The terms ionic activator, and stoichiometric ionic acti carbon atoms, or carbon and silicon atoms, is counted from vator can be used interchangeably. Likewise, the terms neu immediately adjacent to the double bond to immediately tral Stoichiometric activator, and Lewis acid activator can be adjacent to the non-carbon or non-silicon moiety. Examples used interchangeably. include 8,8,8-trifluoro-1-octene, 8-methoxyoct-1-ene, 8-me thylsulfanyloct-1-ene, 8-dimethylaminooct-1-ene, or combi nations thereof. The use of functional group-containing DETAILED DESCRIPTION OF THE C-olefins where the functional group is closer to the double EMBODIMENTS bond is also within the scope of embodiments of the invention when Such olefins may be incorporated in the same manner as 0070 The present invention is directed to a process for are their C-olefin analogs. See, “Metallocene Catalysts and producing Substituted transition metal compounds, prefer Borane Reagents in The Block/Graft Reactions of Polyole ably Substituted metallocene compounds, from precursors fins'. T. C. Chung, etal, Polym. Mater. Sci. Eng., v. 73, p. 463 containing halogen and/or Sulfonate Substituted monocyclic (1995), and the masked C-olefin monomers of U.S. Pat. No. or polyclic ligands, and to the use of the resulting transition 5,153,282. Such monomers permit the preparation of both metal compounds in combination with Suitable activators as functional-group containing copolymers capable of Subse catalysts for the polymerization of olefins, such as ethylene quent derivatization, and of functional macromers which may and propylene. be used as graft and block type polymeric segments. Copo 0071. In one embodiment, the invention relates to a pro lymerization can also incorporate C-olefinic macromono cess for producing a substituted transition metal compound, mers of up to 2000 mer units. the process comprising contacting: (a) a transition metalcom 0064. For purposes of this disclosure, the term oligomer pound comprising at least one ligand having a halogen or refers to compositions having 2-75 mer units and the term sulfonate substituent directly bonded to any sp carbon atom polymer refers to compositions having 76 or more mer units. at a bondable ring position of said ligand, with (b) a transfer A mer is defined as a unit of an oligomer or polymer that agent capable of replacing the halogen or Sulfonate Substitu originally corresponded to the monomer(s) used in the oligo ent of the ligand with a hydrocarbyl, substituted hydrocarbyl, merization or polymerization reaction. For example, the mer halocarbyl, substituted halocarbyl, silylcarbyl, or germylcar of polyethylene would be ethylene. byl Substituent, and (c) a coupling-catalyst. 0065. The term “catalyst system is defined to mean a 0072 Preferably, the transition metal is a Group 3-10 ele catalyst precursor/activator pair. When “catalyst system” is ment, preferably a Group 4 element. used to describe such a pair before activation, it means the 0073 Generally, the halogen or sulfonate substituent on unactivated catalyst (precatalyst) together with an activator the ligand is a chloro, bromo, iodo, tosylate or triflate Sub and, optionally, a co-activator. When it is used to describe stituent, and preferably is a chloro or bromo substituent. US 2010/01 13717 A1 May 6, 2010

0074. In another embodiment, the present invention pro 2-benzofuryl, 3-(N-methylindolyl), phenyl, 2-methylphenyl, vides a process for producing a Substituted metallocene com 3-methylphenyl, 4-methylphenyl, 4-tert-butylphenyl, 2.6- pound, the process comprising: dimethylphenyl, 2,6-diisopropylphenyl, 3,5-dimethylphenyl, (a) providing a first compound represented by the formula (1): 2,5-dimethylphenyl, 3,5-diisopropylphenyl, 3,5-di-tert-bu tylphenyl, 2-isopropylphenyl, 3-trifluoromethylphenyl, AMX, 4-fluorophenyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-dim wherein: ethylaminophenyl, 1-naphthyl 2-naphthyl, and pentafluo M is a transition metal atom having a coordination number of rophenyl. n (preferably 2, 3, 4, 5, or 6) selected from Group 3, 4, 5 or 6 0079. In a further embodiment, the present invention pro of the Periodic Table of Elements, or a lanthanide metal atom, vides a process for producing a Substituted metallocene com or actinide metal atom, preferably a Group 4 transition metal pound, the process comprising: atom selected from titanium, Zirconium or hafnium; (a) providing a first compound represented by the formula (2): A is a monocyclic or polycyclic ligand that is pi-bonded to M and is Substituted with at least one halogen or Sulfonate Sub stituent directly bonded to any sp carbonatomat a bondable ring position of the ligand; and each X is, independently, a univalent anionic ligand, or two X are joined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene wherein ligand, or an alkylidene ligand; and M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanide (b) reacting said first compound with a transfer-agent which metal atom, or actinide metal atom, preferably a Group 4 comprises a hydrocarbyl, Substituted hydrocarbyl, halocar transition metal atom selected from titanium, Zirconium or byl, substituted halocarbyl, silylcarbyl, or germylcarbyl radi hafnium; cal capable of replacing said at least one halogen or Sulfonate each of J and E is independently a substituted or unsubsti Substituent of said first compound under reaction conditions, tuted, monocyclic or polycyclic ligand pi-bonded to M, and in the presence of a coupling-catalyst wherein at least one of Jand E includes at least one halogen or 0075. In a preferred embodiment, the ligand A may be a sulfonate substituent directly bonded to an sp carbonatomat Substituted monocyclic or Substituted polycyclic ligand, pref a bondable ring position of the ligand; erably a substituted monocyclic arenyl or substituted polycy Q is an optional bridging group that is bonded to E and J. and clic arenyl ligand. In another embodiment, the ligand A may is present when y is one and absent wheny is Zero; include one or more ring heteroatoms selected from boron, a y is Zero or one; and Group 14 atom that is not carbon, a Group 15 atom, and a each X is, independently, a univalent anionic ligand, or two X Group 16 atom. Alternately, the ligand A may be selected are joined and bound to the metal atom to form a metallocycle from substituted cyclopentadienyl, substituted heterocyclo ring, or two X are joined to form a chelating ligand, a diene pentadienyl, substituted indenyl, substituted heteroindenyl, ligand, or an alkylidene ligand; and substituted fluorenyl, substituted heterofluorenyl, substituted (b) reacting said first compound with a transfer-agent which cyclopentanaphthyl, Substituted heterocyclopentanaphthyl, comprises a hydrocarbyl, Substituted hydrocarbyl, halocar substituted heterophenyl, substituted heterocyclopentapen byl, substituted halocarbyl, silylcarbyl, germylcarbyl radical talenyl, Substituted heterocyclopentaindenyl, and Substituted capable of replacing said at least one halogen or Sulfonate heterobenzocyclopentaindenyl ligands. Substituent of said first compound under reaction conditions, 0076. In a particularly preferred embodiment ligand A is a and in the presence of a coupling-catalyst. halogenated cylopentadienyl, halogenated indenyl, or halo 0080 Each of the ligands J and E may be a substituted or genated fluorenyl group, preferably a brominated cylopenta unsubstituted monocyclic or polycyclic ligand, provided that dienyl, brominated indenyl, or brominated fluorenyl group. at least J or E is a Substituted moncylclic or polycyclic ligand. 0077 Generally, the halogen or sulfonate substituent of For example, the ligands J and E may each be selected from ligand A is a chloro, bromo, iodo, tosylate or triflate Substitu Substituted or unsubstituted cyclopentadienyl, heterocyclo ent, and preferably is a chloro or bromo substituent. pentadienyl, indenyl, heteroindenyl, fluorenyl, heterofluore 0078. The transfer-agent will normally be an organome nyl, cyclopentanaphthyl, heterocyclopentanaphthyl, het tallic transfer-agent comprising a R***M' unit, where the erophenyl, heterocyclopentapentalenyl, metal M' is selected from boron, tin, magnesium, lithium, heterocyclopentaindenyl, and heterobenzocyclopentaindenyl aluminum, silicon, copper, and zinc, and R*** is selected ligands. In some embodiments, the ligand J and or E may from hydrocarbyl, substituted hydrocarbyl, halocarbyl, sub include one or more ring heteroatoms selected from boron, a stituted halocarbyl, silylcarbyl, or a germylcarbyl radical. Group 14 atom that is not carbon, a Group 15 atom, and a Alternatively, the transfer-agent can be an organic molecule Group 16 atom. In a preferred embodiment, each of J and E is R***H where R*** is selected from hydrocarbyl, substituted independently a Substituted or unsubstituted cyclopentadi hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, enyl ligand, a Substituted or unsubstituted heterocyclopenta or a germylcarbyl radical. Preferred examples of R*** dienyl ligand, a Substituted or unsubstituted indenyl ligand, a include methyl, ethyl, n-propyl, isopropyl. n-butyl, sec-butyl, substituted or unsubstituted heteroindenyl ligand, or a substi isobutyl, tert-butyl, cyclopentyl, cyclohexyl, benzyl, 4-meth tuted or unsubstituted fluorenyl ligand, a substituted or ylbenzyl, 4-methoxybenzyl, 4-trifluoromethyl, diphenylm unsubstituted heterofluorenyl ligand, and a substituted or ethyl, adamantyl, cyclohexenyl, isopropenyl, 2-phenylethe unsubstituted cyclopentanaphthyl, or a Substituted or unsub nyl, trimethylsilylmethyl, neopentyl, methoxymethyl, stituted heterocyclopentanaphthyl ligand, or a Substituted or 3-methoxypropyl, dimethylaminomethyl, diphenylphosphi unsubstituted heterophenyl ligand, or a Substituted or unsub nomethyl 2-pyridyl, 4-pyridyl, 2-thienyl, 2-benzothienyl, stituted heterocyclopentapentalenyl ligand, or a substituted or US 2010/01 13717 A1 May 6, 2010 unsubstituted heterocyclopentaindenyl ligand, or a Substi (a) providing a first compound represented by the formula (3): tuted or unsubstituted heterobenzocyclopentaindenyl ligand. 0081 Generally, the halogen or sulfonate substituent is a chloro, bromo, iodo, tosylate or triflate substituent, and pref erably is a chloro or bromo substituent. 0082 Preferably, Q is present and is a bridging group containing at least one Group 13, 14, 15, or 16 element, in particular boron or a Group 14, 15 or 16 element, and Q can be bonded to any bondable ring position of J and E. Examples of suitable bridging groups include P(=S)R', P(=Se)R', wherein P(=O)R', R'C, R'Si, R'Ge. RCCR, RCCRCR', M is a Group 3, 4, 5 or 6 transition metal atom, or a lanthanide RCCR'CR'CR', RC—CR', RC–CR'CR', metal atom, or actinide metal atom, preferably a Group 4 RCCR'—CR'CR', R'C—CR'CR'—CR', transition metal atom selected from titanium, Zirconium or R'C–CR'CR'CR', RCSiR', R'SiSiR', RCSiR'CR', hafnium; R'SiCR'SiR' R'C—CR'SiR, RCGeR', R'GeGeR', Z is a Substituted or unsubstituted, monocyclic or polycyclic RCGeR'CR', R'GeCR'GeR', R'SiGeR', ligand that is pi-bonded to M: R'C—CR'GeR', RB, RC BR', RC BR-CR', Q' is an optional bridging group that is bonded to Zand T, and R'C O CR's RCRC O CRCR, RC O— is present when y is one and absent wheny is Zero; CR'CR', RC O CR'—CR, RC S CR', y is Zero or one; and R'CR'C S CR'CR', RC S CR'CR', RC S T is a heteroatom with a coordination number of three from CR'—CR', RC Se CR's RCRC Se CR'CR', Group 15 or with a coordination number of two from Group RC Se CRCR', RC Se CR'—CR', RC 16 of the Periodic Table of Elements, and preferably is nitro N=CR', RC NR' CR's RC NR' CR'CR's RC gen, NR CR'—CR, RCRC NR CRCR's RC R" is selected from a C-C substituted or unsubstituted P—CR', RC PR CR' O, S, Se, Te, NR", PR', AsK', monocyclic or polycyclic ring structure Substituent that is SbR', O O, S. S. RN NR', RP PR', O S, O NR', partially unsaturated, unsaturated or aromatic; or a C-Coo O PR', S NR', S PR', and RN PR' where R is hydro Substituted or unsubstituted, unsaturated or partially unsatur gen or a C-C containing hydrocarbyl, Substituted hydro ated, linear or branched alicyclic hydrocarbyl substituent; or carbyl, halocarbyl, Substituted halocarbyl, silylcarbyl or ger a C-Coo substituted or unsubstituted saturated hydrocarbyl mylcarbyl substituent and optionally two or more adjacent R' radical; may join to form a substituted or unsubstituted, Saturated, t is the coordination number of the heteroatom T where “t-1- partially unsaturated or aromatic, cyclic or polycyclic Sub y’ indicates the number of R" substituents bonded to T; and stituent. Preferred examples for the bridging group Q include each X is, independently, a univalent anionic ligand, or two X CH, CHCH, CH(CH), SiMe. SiPh. SiMePh, Si(CH), are joined and bound to the metal atom to form a metallocycle Si(CH), O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, ring, or two X are joined to form a chelating ligand, a diene PPr, and PBu. ligand, or an alkylidene ligand; 0083. The transfer-agent will normally be an organome provided that Z is substituted with at least one halogen or tallic transfer-agent comprising an R***M' unit, where the sulfonate substituent directly bonded to any sp carbonatom metal M' is selected from boron, tin, magnesium, lithium, at a bondable ring position of the ligand Z, or that R" is aluminum, silicon, copper, and zinc, and R*** is selected substituted with at least one halogen or sulfonate substituent from hydrocarbyl, substituted hydrocarbyl, halocarbyl, sub bonded to an sp carbon atom, or both; and stituted halocarbyl, silylcarbyl, or a germylcarbyl radical. (b) reacting said first compound with a transfer-agent which Alternatively, the transfer-agent can be an organic molecule comprises a hydrocarbyl, Substituted hydrocarbyl, halocar R***H where R*** is selected from hydrocarbyl, substituted byl, substituted halocarbyl, silylcarbyl, germylcarbyl radical hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, capable of replacing said at least one halogen or Sulfonate or a germylcarbyl radical. Preferred examples of R*** Substituent of said first compound under reaction conditions, include methyl, ethyl, n-propyl, isopropyl. n-butyl, sec-butyl, and in the presence of a coupling-catalyst. isobutyl, tert-butyl, cyclopentyl, cyclohexyl, benzyl, 4-meth I0085. The ligand Z may be a substituted or unsubstituted ylbenzyl, 4-methoxybenzyl, 4-trifluoromethyl, diphenylm monocyclic or polycyclic ligand. For example, the ligand Z ethyl, adamantyl, cyclohexenyl, isopropenyl, 2-phenylethe may be selected from substituted or unsubstituted cyclopen nyl, trimethylsilylmethyl, neopentyl, methoxymethyl, tadienyl, heterocyclopentadienyl, indenyl, heteroindenyl, 3-methoxypropyl, dimethylaminomethyl, diphenylphosphi fluorenyl, heterofluorenyl, cyclopentanaphthyl, heterocyclo nomethyl 2-pyridyl, 4-pyridyl, 2-thienyl, 2-benzothienyl, pentanaphthyl, heterophenyl, heterocyclopentapentalenyl, 2-benzofuryl, 3-(N-methylindolyl), phenyl, 2-methylphenyl, heterocyclopentaindenyl, and heterobenzocyclopentaindenyl 3-methylphenyl, 4-methylphenyl, 4-tert-butylphenyl, 2.6- ligands. In some embodiments, Z may include one or more dimethylphenyl, 2,6-diisopropylphenyl, 3,5-dimethylphenyl, ring heteroatoms selected from boron, a Group 14 atom that is 2,5-dimethylphenyl, 3,5-diisopropylphenyl, 3,5-di-tert-bu not carbon, a Group 15 atom, and a Group 16 atom. Generally, tylphenyl, 2-isopropylphenyl, 3-trifluoromethylphenyl, the halogen or Sulfonate Substituent on the Z ligand is a 4-fluorophenyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-dim chloro, bromo, iodo, tosylate or triflate substituent, and pref ethylaminophenyl, 1-naphthyl 2-naphthyl, and pentafluo erably is a chloro or bromo substituent. rophenyl. I0086. When R" is a C-C substituted or unsubstituted 0084. In yet a further embodiment, the present invention monocyclic or polycyclic ring structure Substituent that is provides a process for producing a substituted metallocene partially unsaturated, unsaturated or aromatic, and is option compound, the process comprising: ally substituted with a halogen or sulfonate directly bonded to US 2010/01 13717 A1 May 6, 2010 any sp carbonatomata bondable position of the substituent, taenyl, cyclohexacosaheptaenyl, cycloheptacosaheptaenyl, non-limiting examples of R" include all isomers of cycloalk cyclooctacosaheptaenyl, cyclononacosaheptaenyl, cyclotria enes, and all isomers of hydrocarbyl, substituted hydrocarbyl, contaheptaenyl, cyclohexadecaoctaenyl, cycloheptadecaoc halocarbyl, substituted halocarbyl, silylcarbyl, germylcarbyl, taenyl, cyclooctadecaoctaenyl, cyclononadecaoctaenyl, cyc halogen, or polar group (including Sulfonate) Substituted loeicosaoctaenyl, cycloheneicosaoctaenyl, cycloalkanes including: cyclopropenyl, cyclobutenyl, cyclo cyclodocosaoctaenyl, cyclotricosaoctaenyl, cyclotetra pentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cosaoctaenyl, cyclopentacosaoctaenyl, cyclohexacosaoctae cyclononenyl, cyclodecenyl, cycloundecenyl, cyclododece nyl, cycloheptacosaoctaenyl, cyclooctacosaoctaenyl, nyl, cyclotridecenyl, cyclotetradecenyl, cyclopentadecenyl, cyclononacosaoctaenyl, cyclotriacontaoctaenyl, cycloocta cyclohexadecenyl, cycloheptadecenyl, cyclooctadecenyl, decanonaenyl, cyclononadecanonaenyl, cycloeicosanonae cyclononadecenyl, cycloeicosenyl, cycloheneicosenyl, nyl, cycloheneicosanonaenyl, cyclodocosanonaenyl, cyclot cyclodocosenyl, cyclotricosenyl, cyclotetracosenyl, cyclo ricosanonaenyl, cyclotetracosanonaenyl, pentacosenyl, cyclohexacosenyl, cycloheptacosenyl, cyclopentacosanonaenyl, cyclohexacosanonaenyl, cyclohep cyclooctacosenyl, cyclononacosenyl, cyclotriacontenyl, tacosanonaenyl, cyclooctacosanonaenyl, cyclonona cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cyclo cosanonaenyl, cyclotriacontanonaenyl, cycloeicosadecaenyl, heptadienyl, cyclooctadienyl, cyclononadienyl, cyclodecadi cycloheneicosadecaenyl, cyclodocosadecaenyl, cyclotri enyl, cycloundecadienyl, cyclododecadienyl, cyclotridecadi cosadecaenyl, cyclotetracosadecaenyl, cyclopentacosade enyl, cyclotetradecadienyl, cyclopentadecadienyl, caenyl, cyclohexacosadecaenyl, cycloheptacosadecaenyl, cyclohexadecadienyl, cycloheptadecadienyl, cyclooctadeca cyclooctacosadecaenyl, cyclononacosadecaenyl, cyclotria dienyl, cyclononadecadienyl, cycloeicosadienyl, cyclohene contadecaenyl, cyclodocosaundecaenyl, cyclotricosaunde icosadienyl, cyclodocosadienyl, cyclotricosadienyl, cyclotet caenyl, cyclotetracosaundecaenyl, cyclopentacosaundecae racosadienyl, cyclopentacosadienyl, cyclohexacosadienyl, nyl, cyclohexacosaundecaenyl, cycloheptacosaundecaenyl, cycloheptacosadienyl, cyclooctacosadienyl, cyclononacosa cyclooctacosaundecaenyl, cyclononacosaundecaenyl, cyclo dienyl, cyclotriacontadienyl, cyclohexatrienyl, cyclohep triacontaundecaenyl, cyclotetracosadodecaenyl, cyclopenta tatrienyl, cyclooctatrienyl, cyclononatrienyl, cyclodecatri cosadodecaenyl, cyclohexacosadodecaenyl, cycloheptacosa enyl, cycloundecatrienyl, cyclododecatrienyl, dodecaenyl, cyclooctacosadodecaenyl, cyclotridecatrienyl, cyclotetradecatrienyl, cyclopentadecatri cyclononacosadodecaenyl, cyclotriacontadodecaenyl, cyclo enyl, cyclohexadecatrienyl, cycloheptadecatrienyl, cyclooc hexacosamidecaenyl, cycloheptacosamidecaenyl, cycloocta tadecatrienyl, cyclononadecatrienyl, cycloeicosatrienyl, cosamidecaenyl, cyclononacosamidecaenyl, cyclotriaconta cycloheneicosatrienyl, cyclodocosatrienyl, cyclotricosatirie midecaenyl, cyclooctacosatetradecaenyl, nyl, cyclotetracosatrienyl, cyclopentacosatrienyl, cyclohexa cyclononacosatetradecaenyl, cyclotriacontatetradecaenyl, cosatrienyl, cycloheptacosatrienyl, cyclooctacosatrienyl, cyclotriacontapentadecaenyl, and the like; all isomers of cyclononacosatrienyl, cyclotriacontatrienyl, cyclooctatetre polycyclic alkenes, and all isomers of hydrocarbyl, Substi nyl, cyclononatetrenyl, cyclodecatetrenyl, cycloundecatetre tuted hydrocarbyl, halocarbyl, substituted halocarbyl, silyl nyl, cyclododecatetrenyl, cyclotridecatetrenyl, cyclotetrade carbyl, germylcarbyl, halogen, or polar group (including Sul catetrenyl, cyclopentadecatetrenyl, cyclohexadecatetrenyl, fonate) Substituted polycyclic alkenes including: cycloheptadecatetrenyl, cyclooctadecatetrenyl, cyclonona norbornenyl, norbornadienyl spiro4.5 decenyl, spiro5.7 decatetrenyl, cycloeicosatetrenyl, cycloheneicosatetrenyl, tridecenyl, and the like; phenyl, and all isomers of hydrocar cyclodocosatetrenyl, cyclotricosatetrenyl, cyclotetracosate byl, substituted hydrocarbyl, halocarbyl, substituted halocar trenyl, cyclopentacosatetrenyl, cyclohexacosatetrenyl, cyclo byl, silylcarbyl, germylcarbyl, halogen, or polar group heptacosatetrenyl, cyclooctacosatetrenyl, cyclononacosate (including Sulfonate) Substituted phenyl including: meth trenyl, cyclotriacontatetrenyl, cyclodecapentaenyl, ylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphe cycloundecapentaenyl, cyclododecapentaenyl, cyclotrideca nyl, ethylphenyl, diethylphenyl, triethylphenyl, tetraeth pentaenyl, cyclotetradecapentaenyl, cyclopentadecapentae ylphenyl, propylphenyl, dipropylphenyl, tripropylphenyl, nyl, cyclohexadecapentaenyl, cycloheptadecapentaenyl, tetrapropylphenyl, butylphenyl, dibutylphenyl, tributylphe cyclooctadecapentaenyl, cyclononadecapentaenyl, cycloe nyl, tetrabutylphenyl, hexylphenyl, dihexylphenyl, trihexy icosapentaenyl, cycloheneicosapentaenyl, cyclodocosapen lphenyl, tetrahexylphenyl, dimethylethylphenyl, dimethyl taenyl, cyclotricosapentaenyl, cyclotetracosapentaenyl, propylphenyl, dimethylbutylphenyl, dimethylpentylphenyl, cyclopentacosapentaenyl, cyclohexacosapentaenyl, cyclo dimethylhexylphenyl, diethylmethylphenyl, diethylpropy heptacosapentaenyl, cyclooctacosapentaenyl, cyclonona lphenyl, diethylbutylphenyl, diethylpentylphenyl, diethyl cosapentaenyl, cyclotriacontapentaenyl, cyclododecahexae hexylphenyl, dipropylmethylphenyl, dipropylethylphenyl, nyl, cyclotridecahexaenyl, cyclotetradecahexaenyl, dipropylbutylphenyl, dipropylpentylphenyl, dipropylhexy cyclopentadecahexaenyl, cyclohexadecahexaenyl, cyclohep lphenyl, dibutylmethylphenyl, dibutylethylphenyl, dibutyl tadecahexaenyl, cyclooctadecahexaenyl, cyclononadeca propylphenyl, dibutylpentylphenyl, dibutylhexylphenyl, hexaenyl, cycloeicosahexaenyl, cycloheneicosahexaenyl, methylethylphenyl, methylpropylphenyl, methylbutylphe cyclodocosahexaenyl, cyclotricosahexaenyl, cyclotetracosa nyl, methylpentylphenyl, methylhexylphenyl, ethylpropy hexaenyl, cyclopentacosahexaenyl, cyclohexacosahexaenyl, lphenyl, ethylbutylphenyl, ethylpentylphenyl, ethylhexy cycloheptacosahexaenyl, cyclooctacosahexaenyl, lphenyl, propylbutylphenyl, propylpentylphenyl, cyclononacosahexaenyl, cyclotriacontahexaenyl, cyclotet propylhexylphenyl, butylpentylphenyl, butylhexylphenyl, radecaheptaenyl, cyclopentadecaheptaenyl, cyclohexadeca methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphe heptaenyl, cycloheptadecaheptaenyl, cyclooctadecaheptae nyl, pentoxyphenyl, hexoxyphenyl, dimethoxyphenyl, phe nyl, cyclononadecaheptaenyl, cycloeicosaheptaenyl, noxyphenyl, methylmethoxyphenyl, dimethylaminophenyl, cycloheneicosaheptaenyl, cyclodocosaheptaenyl, cyclotri dipropylaminophenyl, bis(dimethylamino)phenyl, methyl cosaheptaenyl, cyclotetracosaheptaenyl, cyclopentacosahep (dimethylamino)phenyl, trimethylsilylphenyl, trimethylger US 2010/01 13717 A1 May 6, 2010 mylphenyl, trifluoromethylphenyl, bis(trifluoromethyl)phe thano. 1,2-dianthracenyletheno and the like; all isomers of nyl, trifluoromethoxyphenyl and the like; benzyl, and all heterocycles, and all isomers of hydrocarbyl, substituted isomers of hydrocarbyl, substituted hydrocarbyl, halocarbyl, hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, Substituted halocarbyl, silylcarbyl, germylcarbyl, halogen, or germylcarbyl, halogen, or polar group (including Sulfonate) polar group (including Sulfonate) Substituted benzyl includ Substituted heterocycles including: acridarsinyl, acridinyl, ing: methylbenzyl, dimethylbenzyl, trimethylbenzyl, tetram acridophosphinyl, 1H-acrindolinyl, anthrazinyl, anthyridi ethylbenzyl, ethylbenzyl, diethylbenzyl, triethylbenzyl, tet nyl, arsanthridinyl, arsindolyl, arsindolizinyl, arsinolinyl, raethylbenzyl, propylbenzyl, dipropylbenzyl, arsinolizinyl, benzofuranyl, carbazolyl, B-carbolinyl, tripropylbenzyl, tetrapropylbenzyl, butylbenzyl, dibutylben chromenyl, thiochromenyl, cinnolinyl, furanyl, imidazolyl, Zyl, tributylbenzyl, tetrabutylbenzyl, hexylbenzyl, dihexyl indazolyl, indolyl, indolizinyl, isoarsindolyl, isoarsinolinyl, benzyl, trihexylbenzyl, tetrahexylbenzyl, dimethylethylben isobenzofuranyl, isochromenyl, isothiochromenyl, isoin Zyl. dimethylpropylbenzyl, dimethylbutylbenzyl, dolyl, isophosphindolyl, isophosphinolinyl, isoquinolinyl, dimethylpentylbenzyl, dimethylhexylbenzyl, diethylmethyl isothiazolyl, isoxazolyl, naphthyridinyl, oxazolyl, perimidi benzyl, diethylpropylbenzyl, diethylbutylbenzyl, diethylpen nyl, phenanthrazinyl, phenanthridinyl, phenanthrolinyl, tylbenzyl, diethylhexylbenzyl, dipropylmethylbenzyl, dipro phenazinyl, phosphanthridinyl, phosphindolyl, phosphin pylethylbenzyl, dipropylbutylbenzyl, dipropylpentylbenzyl, dolizinyl, phosphinolizinyl, phthalazinyl, pteridinyl, phtha dipropylhexylbenzyl, dibutylmethylbenzyl, dibutylethylben loperinyl, purinyl, pyranyl, thiopyranal, pyrazinyl, pyrazolyl, Zyl, dibutylpropylbenzyl, dibutylpentylbenzyl, dibutylhexy pyridazinyl, pyridinyl, pyrindinyl, pyrimidinyl, pyrrolyl, pyr lbenzyl, methylethylbenzyl, methylpropylbenzyl, methylbu rolizinyl, quinazolinyl, quindolinyl, 1H-quinindolinyl, tylbenzyl, methylpentylbenzyl, methylhexylbenzyl, quinolinyl, quinolizinyl, quinoxalinyl, selenophenyl, thebe ethylpropylbenzyl, ethylbutylbenzyl, ethylpentylbenzyl, eth nidinyl, thiazolyl, thiophenyl, triphenodioxazinyl, tripheno ylhexylbenzyl, propylbutylbenzyl, propylpentylbenzyl, pro dithiazinyl, Xanthenyl, chromanyl, thiochromanyl, indolinyl, pylhexylbenzyl, butylpentylbenzyl, butylhexylbenzyl, meth isochromanyl, isothiochromanyl, isoindolinyl, bipyridyl, oxybenzyl, ethoxybenzyl, propoxybenzyl, butoxybenzyl, pyrido 2, 1,6-dequinolizinyl and the like. pentoxybenzyl, hexoxybenzyl, dimethoxybenzyl, phenoxy I0087. When R" a C-C substituted or unsubstituted, benzyl, methylmethoxybenzyl, dimethylaminobenzyl, dipro unsaturated or partially unsaturated, linear or branched alicy pylaminobenzyl, bis(dimethylamino)benzyl, methyl(dim clic hydrocarbyl substituent, and is optionally substituted ethylamino)benzyl, trifluoromethylbenzyl, bis with a halogen or sulfonate directly bonded to any sp carbon (trifluoromethylbenzyl), trifluoromethyoxybenzyl, atom at a bondable position of the substituent, non-limiting trimethylsilylbenzyl, bis(trimethylsilyl)benzyl, trimethylger examples of R" include all isomers of alkenes and all isomers mylbenzyl and the like; all isomers of polycyclic areneyls, of hydrocarbyl, substituted hydrocarbyl, halocarbyl, substi and all isomers of hydrocarbyl, substituted hydrocarbyl, halo tuted halocarbyl, silylcarbyl, germylcarbyl, halogen, or polar carbyl, substituted halocarbyl, silylcarbyl, germylcarbyl, group (including Sulfonate) Substituted alkenes including: halogen, or polar group (including Sulfonate) Substituted ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octe polycyclic areneyls including: aceanthrylenyl, acenaphthyl nyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tet ene, acephenanthrylenyl, anthracenyl, aZulenyl, biphenyle radecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octade nyl, chrysenyl, coronenyl, fluoranthenyl, fluorenyl, heptace cenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, nyl, heptalenyl, heptaphenyl, hexacenyl, hexaphenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, hepta as-indacenyl, S-indecenyl, indenyl, naphthalenyl, ovalenyl, cosenyl, octacosenyl, nonacosenyl, triacontenyl, butadienyl, pentacenyl, pentalenyl, pentaphenyl, perylenyl, phenalenyl, pentadienyl, hexadienyl, heptadienyl, octadienyl, nonadie phenanthrenyl, picenyl, pleiadenyl, pyranthrenyl, pyrenyl, nyl, decadienyl, undecadienyl, dodecadienyl, tridecadienyl, rubicenyl, naphthacenyl, tetraphenylenyl, trinaphthylenyl, tetradecadienyl, pentadecadienyl, hexadecadienyl, hepta triphenylenyl, hexahelicenyl, dibenzaa.hanthracenyl, inda decadienyl, octadecadienyl, nonadecadienyl, eicosadienyl, nyl, cholanthrenyl, aceanthrenyl, acephenanthrenyl, 1.2.3,4- heneicosadienyl, docosadienyl, tricosadienyl, tetracosadi tetrahydronaphthalenyl, 5,6-didehydro azulenyl, 1,4-dihy enyl, pentacosadienyl, hexacosadienyl, heptacosadienyl, dronaphthalenyl, 5H-cyclobute indenyl, cycloheptajk octacosadienyl, nonacosadienyl, triacontadienyl, hexatrie phenanthrenyl, benzelacephenanthrylenyl, octalenyl, nyl, heptatrienyl, octatrienyl, nonatrienyl, decatrienyl, unde pentalene 1,6-cdpentalenyl, cyclobutclindenyl, cyclopenta catrienyl, dodecatrienyl, tridecatrienyl, tetradecatrienyl, pen 1 phenanthrene, naphtha2, 1,8-cdeaZulene, fullerenyl and tadecatrienyl, hexadecatrienyl, heptadecatrienyl, the like; all isomers of substituted ring assemblies, and all octadecatrienyl, nonadecatrienyl, eicosatrienyl, heneicosa isomers of hydrocarbyl, substituted hydrocarbyl, halocarbyl, trienyl, docosatrienyl, tricosatrienyl, tetracosatrienyl, penta Substituted halocarbyl, silylcarbyl, germylcarbyl, halogen, or cosatrienyl, hexacosatrienyl, heptacosatrienyl, octacosatirie polar group (including Sulfonate) Substituted ring assemblies nyl, nonacosatrienyl, triacontatrienyl, octatetrenyl, including: biphenyl, terphenyl, binaphthyl, binorbornenyl, nonatetrenyl, decatetrenyl, undecatetrenyl, dodecatetrenyl, phenyl-terphenyl, phenyl-naphthyl, phenyl-anthracenyl, phe tridecatetrenyl, tetradecatetrenyl, pentadecatetrenyl, hexade nyl-phenanthrenyl, bianthracenyl, biphenanthrenyl, and the catetrenyl, heptadecatetrenyl, octadecatetrenyl, nonadecate like; all isomers of bridged monocyclic and polycyclic are trenyl, eicosatetrenyl, heneicosatetrenyl, docosatetrenyl, tri nyls, and all isomers of hydrocarbyl, substituted hydrocarbyl, cosatetrenyl, tetracosatetrenyl, pentacosatetrenyl, halocarbyl, substituted halocarbyl, silylcarbyl, germylcarbyl, hexacosatetrenyl, heptacosatetrenyl, octacosatetrenyl, nona halogen, or polar group (including Sulfonate) Substituted cosatetrenyl, triacontatetrenyl, decapentaenyl, undecapen bridged monocyclic and polycyclic arenyls including: 1,1- taenyl, dodecapentaenyl, tridecapentaenyl, tetradecapentae diphenylmethano. 1,2-diphenylethano. 1,2-diphenyletheno, nyl, pentadecapentaenyl, hexadecapentaenyl, 1.2-dinaphthylethano. 1,2-dinaphthyletheno. 1,1-dinaphth heptadecapentaenyl, octadecapentaenyl, nonadecapentaenyl, ylmethano. 1,1-dianthracenylmethano. 1,2-dianthracenyle eicosapentaenyl, heneicosapentaenyl, docosapentaenyl, tri US 2010/01 13717 A1 May 6, 2010 14 cosapentaenyl, tetracosapentaenyl, pentacosapentaenyl, Syl, perfluorodocosyl, perfluorotricosyl, perfluorotetracosyl, hexacosapentaenyl, heptacosapentaenyl, octacosapentaenyl, perfluoropentacosyl, perfluorohexacosyl, perfluoroheptaco nonacosapentaenyl, triacontapentaenyl, dodecahexaenyl, Syl, perfluorooctacosyl, perfluorononacosyl, and perfluorot tridecahexaenyl, tetradecahexaenyl, pentadecahexaenyl, riacontyl; fluoromethyl, and all isomers of fluoroethyl, fluo hexadecahexaenyl, heptadecahexaenyl, octadecahexaenyl, ropropyl. fluorobutyl, fluoropentyl, fluorohexyl, nonadecahexaenyl, eicosahexaenyl, heneicosahexaenyl, fluoroheptyl, fluorooctyl, fluorononyl, fluorodecyl, perfluo docosahexaenyl, tricosahexaenyl, tetracosahexaenyl, penta roundecyl, fluoro dodecyl, fluorotridecyl, fluorotetradecyl, cosahexaenyl, hexacosahexaenyl, heptacosahexaenyl, octa fluoropentadecyl, fluorohexadecyl, fluoroheptadecyl, fluo cosahexaenyl, nonacosahexaenyl, triacontahexaenyl, tet rooctadecyl, fluorononadecyl, fluoroeicosyl, fluoroheneico radecaheptaenyl, pentadecaheptaenyl, hexadecaheptaenyl, syl, fluorodocosyl, fluorotricosyl, fluorotetracosyl, fluoro heptadecaheptaenyl, octadecaheptaenyl, nonadecaheptaenyl, pentacosyl, fluorohexacosyl, fluoroheptacosyl, eicosaheptaenyl, heneicosaheptaenyl, docosaheptaenyl, tri fluorooctacosyl, fluorononacosyl, and fluorotriacontyl; meth cosaheptaenyl, tetracosaheptaenyl, pentacosaheptaenyl, oxymethyl, ethoxymethyl, and all isomers of methoxyethyl, hexacosaheptaenyl, heptacosaheptaenyl, octacosaheptaenyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxy nonacosaheptaenyl, triacontaheptaenyl, hexadecaoctaenyl, hexyl, methoxyheptyl, methoxyoctyl, methoxynonyl, meth heptadecaoctaenyl, octadecaoctaenyl, nonadecaoctaenyl, Oxydecyl, methoxyundecyl, methoxydodecyl, methoxytride eicosaoctaenyl, heneicosaoctaenyl, docosaoctaenyl, tri cyl, methoxytetradecyl. methoxypentadecyl. cosaoctaenyl, tetracosaoctaenyl, pentacosaoctaenyl, hexa methoxyhexadecyl, methoxyheptadecyl, methoxyoctadecyl. cosaoctaenyl, heptacosaoctaenyl, octacosaoctaenyl, nona methoxynonadecyl, methoxyeicosyl, methoxyheneicosyl, cosaoctaenyl, triacontaoctaenyl, octadecanonaenyl, methoxydocosyl, methoxytricosyl, methoxytetracosyl, nonadecanonaenyl, eicosanonaenyl, heneicosanonaenyl, methoxypentacosyl, methoxyhexacosyl, methoxyheptaco docosanonaenyl, tricosanonaenyl, tetracosanonaenyl, penta Syl, methoxyoctacosyl, methoxynonacosyl, methoxytriacon cosanonaenyl, hexacosanonaenyl, heptacosanonaenyl, octa tyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, cosanonaenyl, nonacosanonaenyl, triacontanonaenyl, eicosa ethoxyhexyl, ethoxyheptyl, ethoxyoctyl, ethoxynonyl, decaenyl, heneicosadecaenyl, docosadecaenyl, ethoxydecyl ethoxyundecyl ethoxydodecyl ethoxytridecyl. tricosadecaenyl, tetracosadecaenyl, pentacosadecaenyl, ethoxytetradecyl ethoxypentadecyl ethoxyhexadecyl. hexacosadecaenyl, heptacosadecaenyl, octacosadecaenyl, ethoxyheptadecyl ethoxyoctadecyl ethoxynonadecyl. nonacosadecaenyl, triacontadecaenyl, docosaundecaenyl, ethoxyeicosyl, ethoxyheneicosyl, ethoxydocosyl, ethoxytri tricosaundecaenyl, tetracosaundecaenyl, pentacosaundecae cosyl, ethoxytetracosyl, ethoxypentacosyl, ethoxyhexacosyl, nyl, hexacosaundecaenyl, heptacosaundecaenyl, octacosaun ethoxyheptacosyl, ethoxyoctacosyl, ethoxynonacosyl, decaenyl, nonacosaundecaenyl, triacontaundecaenyl, tetra ethoxytriacontyl, propoxymethyl, propoxyethyl, pro cosadodecaenyl, pentacosadodecaenyl, poxypropyl, propoxybutyl, propoxypentyl, propoxyhexyl, hexacosadodecaenyl, heptacosadodecaenyl, octacosadode propoxyheptyl, propoxyoctyl, propoxynonyl, propoxydecyl. caenyl, nonacosadodecaenyl, triacontadodecaenyl, hexa propoxyundecyl, propoxydodecyl, propoxytridecyl, pro cosamidecaenyl, heptacosamidecaenyl, octacosamidecaenyl, poxytetradecyl, propoxypentadecyl, propoxyhexadecyl, pro nonacosamidecaenyl, triacontamidecaenyl, octacosatetrade poxyheptadecyl, propoxyoctadecyl, propoxynonadecyl, pro caenyl, nonacosatetradecaenyl, triacontatetradecaenyl, tria poxyeicosyl, propoxyheneicosyl, propoxydocosyl, contapentadecaenyl, cyclopentylidene, cyclohexylidene, propoxytricosyl, propoxytetracosyl, propoxypentacosyl, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclo propoxyhexacosyl, propoxyheptacosyl, propoxyoctacosyl, decylidene, cycloundecylidene, cyclododecylidene, and the propoxynonacosyl, propoxytriacontyl, butoxymethyl, like. butoxyethyl, butoxypropyl, butoxybutyl, butoxypentyl, 0088. When R" is a C-C substituted or unsubstituted butoxyhexyl, butoxyheptyl, butoxyoctyl, butoxynonyl, saturated hydrocarbyl radical, non-limiting examples of R" butoxydecyl, butoxyundecyl, butoxydodecyl, butoxytridecyl, include methyl, ethyl, and all isomers of propyl, butyl, pentyl, butoxytetradecyl, butoxypentadecyl, butoxyhexadecyl. hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl butoxyheptadecyl, butoxyoctadecyl, butoxynonadecyl. tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl butoxyeicosyl, butoxyheneicosyl, butoxydocosyl, butoxytri nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, cosyl, butoxytetracosyl, butoxypentacosyl, butoxyhexacosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and butoxyheptacosyl, butoxyoctacosyl, butoxynonacosyl, and triacontyl; cyclopropyl, and all isomers of cyclobutyl, cyclo butoxytriacontyl; dimethylaminomethyl, and all isomers of pentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, dimethylaminoethyl, dimethylaminopropyl, dimethylami cyclodecyl cycloundecyl cyclododecyl cyclotridecyl nobutyl, dimethylaminopentyl, dimethylaminohexyl, dim cyclotetradecyl, cyclopentadecyl cyclohexadecyl cyclohep ethylaminoheptyl, dimethylaminooctyl, dimethylaminon tadecyl cyclooctadecyl cyclononadecyl, cycloeicosyl, onyl, dimethylaminodecyl. dimethylaminoundecyl. cycloheneicosyl, cyclodocosyl, cyclotricosyl, cyclotetraco dimethylaminododecyl, dimethylaminotridecyl, dimethy Syl, cyclopentacosyl, cyclohexacosyl, cycloheptacosyl, laminotetradecyl, dimethylaminopentadecyl, dimethylami cyclooctacosyl, cyclononacosyl, and cyclotriacontyl; all iso nohexadecyl, dimethylaminoheptadecyl, dimethylaminooc mers of norbornyl, adamantyl, Cubanyl, prismanyl, and spiro tadecyl, dimethylaminononadecyl, dimethylaminoeicosyl, 4.5 decanyl; pefluoromethyl, perfluoroethyl, and all isomers dimethylaminoheneicosyl, dimethylamino docosyl, dim of perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluo ethylaminotricosyl, dimethylaminotetracosyl, dimethylami rohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, per nopentacosyl, dimethylaminohexacosyl, dimethylaminohep fluorodecyl, perfluoroundecyl, perfluorododecyl, perfluorot tacosyl, dimethylaminooctacosyl, dimethylaminononacosyl, ridecyl, perfluorotetradecyl, perfluoropentadecyl. and dimethylaminotriacontyl; trimethylsilylmethyl, and all perfluorohexadecyl, perfluoroheptadecyl, perfluorooctade isomers of trimethylsilylethyl, trimethylsilylpropyl, trimeth cyl, perfluorononadecyl, perfluoroeicosyl, perfluoroheneico ylsilylbutyl, trimethylsilylpentyl, trimethylsilylhexyl, trim US 2010/01 13717 A1 May 6, 2010

ethylsilylheptyl, trimethylsilyloctyl, trimethylsilylnonyl, tri or aromatic, cyclic or polycyclic substituent. Preferred methylsilyldecyl, trimethylsilylundecyl examples for the bridging group Q' include CH, CH2CH2. trimethylsilyldodecyl, trimethylsilyltridecyl, trimethylsi CH(CH), SiMe. SiPh, SiMePh, Si(CH), and Si(CH). lyltetradecyl, trimethylsilylpentadecyl, trimethylsilylhexa 0093. The transfer-agent will normally be an organome decyl, trimethylsilylheptadecyl, trimethylsilyloctadecyl, tri tallic transfer-agent comprising a R***M' fragment, where methylsilylnonadecyl. trimethylsilyleicosyl, the metal M' is selected from boron, tin, magnesium, lithium, trimethylsilylheneicosyl, trimethylsilyldocosyl, trimethylsi aluminum, silicon, copper, and zinc, and R*** is selected lyltricosyl, trimethylsilyltetracosyl, trimethylsilylpentaco from hydrocarbyl, substituted hydrocarbyl, halocarbyl, sub Syl, trimethylsilylhexacosyl, trimethylsilylheptacosyl, trim stituted halocarbyl, silylcarbyl, or a germylcarbyl radical. ethylsilyloctacosyl, trimethylsilylnonacosyl, and Alternatively, the transfer-agent can be an organic molecule trimethylsilyltriacontyl; trimethylgermylmethyl, and all iso R***H where R*** is selected from hydrocarbyl, substituted mers of trimethylgermylethyl, trimethylgermylpropyl, trim hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, ethylgermylbutyl, trimethylgermylpentyl, trimethylgermyl or a germylcarbyl radical. Preferred examples of R*** hexyl, trimethylgermylheptyl, trimethylgermyloctyl, include methyl, ethyl, n-propyl, isopropyl. n-butyl, sec-butyl, trimethylgermylnonyl, trimethylgermyldecyl, trimethylger isobutyl, tert-butyl, cyclopentyl, cyclohexyl, benzyl, 4-meth mylundecyl, trimethylgermyldodecyl, trimethylgermyltride ylbenzyl, 4-methoxybenzyl, 4-trifluoromethyl, diphenylm cyl, trimethylgermyltetradecyl, trimethylgermylpentadecyl ethyl, adamantyl, cyclohexenyl, isopropenyl, 2-phenylethe trimethylgermylhexadecyl, trimethylgermylheptadecyl, tri nyl, trimethylsilylmethyl, neopentyl, methoxymethyl, methylgermyloctadecyl, trimethylgermylnonadecyl, trim 3-methoxypropyl, dimethylaminomethyl, diphenylphosphi ethylgermyleicosyl, trimethylgermylheneicosyl, trimeth nomethyl 2-pyridyl, 4-pyridyl, 2-thienyl, 2-benzothienyl, ylgermyldocosyl, trimethylgermyltricosyl, 2-benzofuryl, 3-(N-methylindolyl), phenyl, 2-methylphenyl, trimethylgermyltetracosyl, trimethylgermylpentacosyl, trim 3-methylphenyl, 4-methylphenyl, 4-tert-butylphenyl, 2.6- ethylgermylhexacosyl, trimethylgermylheptacosyl, trimeth dimethylphenyl, 2,6-diisopropylphenyl, 3,5-dimethylphenyl, ylgermyloctacosyl, trimethylgermylnonacosyl, and trimeth 2,5-dimethylphenyl, 3,5-diisopropylphenyl, 3,5-di-tert-bu ylgermyltriacontyl. tylphenyl, 2-isopropylphenyl, 3-trifluoromethylphenyl, 0089. When the halogen or sulfonate substituent is not on 4-fluorophenyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-dim R", preferably, R" is selected from methyl, ethyl, all propyl ethylaminophenyl, 1-naphthyl 2-naphthyl, and pentafluo isomers, all butyl isomers, phenyl, benzyl, phenethyl, 1-ada rophenyl. mantyl, cyclododecyl cyclohexyl and norbornyl. I0094) Different cross-coupling reactions can be used to 0090 When the halogen or sulfonate substituent is on R", produce Substituted metallocene compounds according to the preferably, R" is selected from 2-bromophenyl, 3-bromophe process described herein. Generic reaction schemes for cou nyl, 4-bromophenyl, 2,6-diisopropyl-4-bromophenyl, 2.6- pling reactions are illustrated below where M, X, y, and R*** dimethyl-4-bromophenyl, 2,4,6-trimethyl-3-bromophenyl, are as previously defined, Y is Q or Q' as previously defined 2-bromo-4,6-dimethylphenyl, 2-bromo-4-methylphenyl, (in the following formulae, Y is not yttrium) and X* is X* is 2-bromo-3,4,6-trimethylphenyl, 2-bromo-4-fluorophenyl, chloro, bromo, iodo or sulfonate (sulfonate=OSOG where 2-bromo-4,6-difluorophenyl, 2,6-dibromophenyl, 2,6-di G is a hydrocarbyl or halocarbyl): bromo-4-methylphenyl, 2,6-dibromo-4-fluorophenyl, 2,5-di bromophenyl, and 2,4-dibromophenyl. 0091 Conveniently, in formula (3), t-1-y is equal to 1 and ligand-X* X transfer-agent ligand-R*** X preferably T is a nitrogen atom. NY --coupling-catalyst NY / N optional additive / N 0092 Conveniently, Q' in formula (3) is present and is a X X solvent X X bridging group containing at least one Group 13, 14, 15, or 16 ligand-X*gan N X transfer-agent ligand-R**gan N X element, in particular boron or a Group 14, 15 or 16 element, Y, M? coupling-catalyst Y, M^ and Q in formula (3) can be bonded to any bondable ring N Heoptional additive / N position of Z. Examples of Suitable bridging groups include ligand-X* X solvent ligand-R*** X P(=S)R, P(=Se)R', P(=O)R', RC, R,Si, R'Ge. ligand-X* X transfer-agent ligand-R*** X RCCR's RCCR'CR's RCCR'CR'CR', R'C—CR', N / coupling-catalyst N / Y M Heoptional additive Y, M RC–CR'CR, RCCR'—CR'CR, RC–CRCR'—CR', / Yx solvent / Yx R'C–CR'CR'CR's RC SiR R'SiSiR', RCSiR'CR', ligand ligand R'SiCR'SiR' R'C—CR'SiR, RCGeR', R'GeGeR', Essentially, the processes described above for producing the Substituted transition metal compounds, particularly Substi tuted metallocene compounds, involve a coupling reaction or R'CR'C S CR'CR', RC S CR'CR', RC S cross-coupling reaction in which a transfer-agent comprising CR'—CR', RC Se CR's RCRC Se CR'CR', aR***Munit, oran organic molecule R***H, is reacted with RC Se CRCR', RC Se CR'—CR', RC ana transition metal compound comprising at least one ligand N=CR, RC NR CR, RC NR CRCR, RC having a halogen or Sulfonate Substituent directly bonded to NR' CR'—CR', RCR'C NR' CRCR's RC any sp carbonatomata bondable ring position of said ligand, P—CR', and RCPR'CR', where R is hydrogen or a C-C, where said substituted ligand is represented by ligand-X* containing hydrocarbyl, Substituted hydrocarbyl, halocarbyl, where X* is chloro, bromo, iodo or sulfonate (sulfonate substituted halocarbyl, silylcarbyl or germylcarbyl substitu —OSOG where G is a hydrocarbylor halocarbyl), usually in ent and optionally two or more adjacent R' may join to form the presence of a coupling-catalyst or combination of cou a substituted or unsubstituted, saturated, partially unsaturated pling-catalysts and, when required, in the presence of addi US 2010/01 13717 A1 May 6, 2010

tives, to produce a substituted transition metal compound When the bridge, Y, is P(R***), where R*** is as defined wherein the ligand(s) of said substituted transition metal above, it is first oxidized to P(=O)R*** using air or another compound is represented by ligand-R***. The transfer-agent, Soft oxidizing agent. After the Negishi coupling reaction, the comprising a R***M' unit, contains the nucleophile R*** to bridge, P(=O)R***, is reduced back to P(R***) using be transferred to ligand-X, as well as a metal-containing trichlorosilane. Alternatively, the bridge, P(R***), can be fragment M. Typical metals “M” useful herein include Al, reacted with elemental sulfur or selenium to form the respec Zr, Si, B, Li, Mg, Sn, Cu, Zn, and mixtures thereof. R*** is tive P(=S)R*** and P(=Se)R*** bridges. After the Negishi substituted or unsubstituted hydrocarbyl, substituted or coupling reaction, the P(=S)R*** and P(=Se)R*** bridges unsubstituted halocarbyl, substituted or unsubstituted silyl can be reduced back to P(R***) using trichlorosilane. carbyl, or substituted or unsubstituted germylcarbyl radical. 0097 Palladium coupling-catalysts that may be used in Ligand-X* includes, but is not limited to substituted or the Negishi coupling reaction on a metallocene include bis unsubstituted cyclopentadienyl, heterocyclopentadienyl, (tri-tert-butyl)phosphine palladium, bis(tricyclohexylphos indenyl, heteroindenyl, fluorenyl, heterofluorenyl, cyclopen phine) palladium, trans-dichlorbis(tricyclohexylphosphine) tanaphthyl, heterocyclopentanaphthyl, heterophenyl, hetero palladium(II), trans-dichlorbis(triphenylphosphine) palla cyclopentapentalenyl, heterocyclopentaindenyl, and heter dium(II), trans-dichlorbis(tri-o-tolylphosphine) palladium obenzocyclopentaindenyl ligands. Additionally, ligand-X* (II), tetrakis(triphenylphosphine)palladium (O), dichloro1, may comprise Substituted or unsubstituted monocyclic or 1'-bis(diphenylphosphino) ferrocenepalladium (II), or polycyclic ring structure Substituents that are partially unsat palladium compounds such as palladium(II) acetate, palla urated, unsaturated or aromatic; or may comprise Substituted dium(0) dibenzylideneacetone, palladium (II) chloride, pal or unsubstitued, unsaturated or partially unsaturated, linear or ladium (II) bromide, palladium (II) iodide, allyl palladium branched alicyclic hydrocarbyl Substituents. Coupling-catal chloride dimer, palladium (II) trifluoroacetate, bis(tri-o- Syts are catalytic reagents that promote the reaction and are tolylphoshine)palladium (II) chloride, dichloro(1,5-cyclooc typically selected from nickel, palladium, copper, silver and tadiene) palladium (II), dichlorobis(benzonitrile) palladium cobalt compounds. The additives are compounds that (II), dichlorobis(acetonitrile) palladium (II), bis(2-methylal enhance the coupling reaction by, for example, increasing lyl) palladium chloride dimer, crotyl palladium chloride regioselectivity, increasing enantioselectivity, Suppressing dimer, tris(dibenzylideneacetone) dipalladium (O), or dichlo undesired side reactions, activating the coupling-catalyst or robis(benzonitrile)palladium (II) used in combination with other reagents, regenerating the coupling-catalyst, stabilizing any of the phosphine and phosphine like reagents (A through the coupling-catalyst or intermediates, coordinating counte N) listed below. When the metallocene is substituted with an rions, or accelerating the coupling reaction. iodo ligand, any of the palladium compounds listed above 0095 Different cross-coupling reactions can be used to will work to catalyze the coupling reaction even in the produce Substituted metallocene compounds according to the absence of phosphine and phosphine like reagents. process described herein. For example, the Negishi coupling 0.098 Preferred palladium coupling-catalysts that may be reaction uses a substituted or unsubstituted hydrocarbyl Zinc used in the Negishi coupling reaction on a metallocene transfer-agent (R***ZnX* or R*** Zn where X* is chlo include bis(tri-tert-butyl)phosphine palladium, or palladium ride, bromide or iodide, and R*** is substituted or unsubsti (II) acetate, palladium(0) dibenzylideneacetone used in com tuted hydrocarbyl, substituted or unsubstituted halocarbyl, bination with any of the phosphine and phosphine like substituted or unsubstituted silylcarbyl, or substituted or reagents (A through N) listed below. unsubstituted germylcarbyl radical) with a palladium cou 0099 Organozinc reagents, R***ZnX** or R*** Zn, that pling-catalyst Such as bis(tri-tert-butylphosphine)palladium may be used in the Negishi coupling reaction are those where to react with bromine substituent(s) on the metallocene X** selected from chloride, bromide or iodide, and where according to the following reactions (where X*, M, X, R***, R*** is, independently, selected from X**, and y are as defined above and Y is as defined for Q and (a) hydrocarbyls and all isomers of hydrocarbyls including Q' (in the following formulae, Y is not yttrium)): methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl. tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl. ligand X*X-k x R***ZnxiPod catalyst is or R***Zn ligand-R**** X nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, NY y / pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, x^ Yy THF / M N triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, X X ligand X* x R***ZnX** or R** Zn ligand-R*** X octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, NY Pd catalyst J. N / tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octa --- decenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, ligandx:* /'N X THF ligand /\Xe X tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, hepta ligand X* R***ZnX** or R* * * Zn ligand-R*** cosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, N X Pd catalyst y N X butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, y M y M decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, 1 N THF | 1 N pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, ligand X ligand X nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosy nyl, tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, 0096. After reaction, trimethylsilyl chloride is added to octacosynyl. nonacosynyl, and triacontynyl: react with excess organozinc transfer-agent present. The (b) halocarbyls and all isomers of halocarbyls including per entire reaction mixture is then evaporated to dryness and fluoropropyl, perfluorobutyl, perfluoropentyl, perfluoro tetrahydrofuran (THF) contamination of the metallocene hexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, per product is eliminated by refluxing the metallocene in toluene. fluorodecyl, perfluoroundecyl perfluorododecyl, US 2010/01 13717 A1 May 6, 2010 17 perfluorotridecyl, perfluorotetradecyl, perfluoropentadecyl dimethylaminopentacosyl, dimethylaminohexacosyl, dim perfluorohexadecyl, perfluoroheptadecyl, perfluorooctade ethylaminoheptacosyl, dimethylaminooctacosyl, dimethy cyl, perfluorononadecyl, perfluoroeicosyl, perfluoroheneico laminononacosyl, dimethylaminotriacontyl, methoxybenzyl, Syl, perfluorodocosyl, perfluorotricosyl, perfluorotetracosyl, ethoxybenzyl, propoxybenzyl, butoxybenzyl, methoxyphe perfluoropentacosyl, perfluorohexacosyl, perfluoroheptaco nyl, ethoxyphenyl, propyoxyphenyl, butoxyphenyl, dimethy Syl, perfluorooctacosyl, perfluorononacosyl, perfluorotria laminobenzyl, diethylaminobenzyl, dipropylaminobenzyl, contyl, perfluorobutenyl, perfluorobutynyl, fluoropropyl. dibutylaminobenzyl, dimethylaminophenyl, diethylami fluorobutyl, fluoropentyl, fluorohexyl, fluoroheptyl, fluo nophenyl, dipropylaminophenyl, dibutylaminophenyl, meth rooctyl, fluorononyl, fluorodecyl, fluoroundecyl, fluorodode ylthiobenzyl, ethylthiobenzyl, propylthiobenzyl, butylth cyl, fluorotridecyl, fluorotetradecyl, fluoropentadecyl, fluo iobenzyl, methylthiophenyl, ethylthiophenyl, rohexadecyl. fluoroheptadecyl, fluorooctadecyl. propylthiophenyl, butylthiophenyl, dimethylphosphinoben fluorononadecyl, fluoroeicosyl, fluoroheneicosyl, fluoro Zyl, diethylphosphinobenzyl, dipropylphosphinobenzyl, docosyl, fluorotricosyl, fluorotetracosyl, fluoropentacosyl, dibutylphosphinobenzyl, methoxychlorophenyl, methoxy fluorohexacosyl, fluoroheptacosyl, fluorooctacosyl, fluo bromophenyl, methoxyiodophenyl, methoxyfluorophenyl, rononacosyl, fluorotriacontyl, difluorobutyl, trifluorobutyl, ethoxychlorophenyl, ethoxybromophenyl, ethoxyiodophe tetrafluorobutyl, pentafluorobutyl, hexafluorobutyl, hep nyl, ethoxyfluorophenyl, propoxychlorophenyl, propoxybro tafluorobutyl, octafluorobutyl: mophenyl, propoxyiodophenyl, propoxyfluorophenyl, (c) substituted hydrocarbyl radicals and all isomers of substi butoxychlorophenyl, butoxybromophenyl, butoxyiodophe tuted hydrocarbyl radicals including methoxymethyl, meth nyl, butoxyfluorophenyl, dimethylchloroaminophenyl, dieth oxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, ylchloroaminophenyl, dipropoxychlorophenyl, dibutoxy methoxyhexyl, methoxyheptyl, methoxyoctyl, methox chlorophenyl, dimethylbromoaminophenyl, ynonyl, methoxydecyl, methoxyundecyl, methoxydodecyl. diethylbromoaminophenyl, dipropoxybromophenyl, dibu methoxytridecyl, methoxytetradecyl, methoxypentadecyl toxybromophenyl, dimethyliodoaminophenyl, dieth methoxyhexadecyl, methoxyheptadecyl, methoxyoctadecyl yliodoaminophenyl, dipropoxyiodophenyl, dibutoxy methoxynonadecyl, methoxyeicosyl, methoxyheneicosyl, iodophenyl, dimethylfluoroaminophenyl, methoxydocosyl, methoxytricosyl, methoxytetracosyl, diethylfluoroaminophenyl, dipropoxyfluorophenyl, dibu methoxypentacosyl, methoxyhexacosyl, methoxyheptaco toxyfluorophenyl, dimethylaminochlorophenyl, diethylami Syl, methoxyoctacosyl, methoxynonacosyl, methoxytriacon nochlorophenyl, dipropylaminochlorophenyl, dibutylami tyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, nochlorophenyl, dimethylaminobromophenyl, ethoxypentyl, ethoxyhexyl, ethoxyheptyl, ethoxyoctyl, diethylaminobromophenyl, dipropylaminobromophenyl, ethoxynonyl, ethoxydecyl ethoxyundecyl ethoxydodecyl. dibutylaminobromophenyl, dimethylaminoiodophenyl, ethoxytridecyl ethoxytetradecyl ethoxypentadecyl ethoxy diethylaminoiodophenyl, dipropylaminoiodophenyl, dibuty hexadecyl ethoxyheptadecyl, methoxyoctadecyl ethox laminoiodophenyl, dimethylaminofluorophenyl, diethylami ynonadecyl ethoxyeicosyl, ethoxyheneicosyl, ethoxydoco nofluorophenyl, dipropylaminofluorophenyl, dibutylaminof Syl, ethoxytricosyl, ethoxytetracosyl, ethoxypentacosyl, luorophenyl, methylthiochlorophenyl, ethoxyhexacosyl, ethoxyheptacosyl, methoxyoctacosyl, ethylthiochlorophenyl, propylthiochlorophenyl, butylthio ethoxynonacosyl, ethoxytriacontyl, propoxymethyl, pro chlorophenyl, methylthiobromophenyl, ethylthiobromophe poxyethyl, propoxypropyl, propoxybutyl, propoxypentyl, nyl, propylthiobromophenyl, butylthiobromophenyl, meth propoxyhexyl, propoxyheptyl, propoxyoctyl, propoxynonyl, ylthioiodophenyl, ethylthioiodophenyl, propoxy decyl, propoxyundecyl, propoxydodecyl, pro propylthioiodophenyl, butylthioiodophenyl, methylthiofluo poxytridecyl, propoxytetradecyl, propoxypentadecyl, pro rophenyl, ethylthiofluorophenyl, propylthiofluorophenyl, poxyhexadecyl, propoxyheptadecyl, mpropoxyoctadecyl butylthiofluorophenyl, benzoyl acid methyl ester, benzoyl propoxynonadecyl, propoxyeicosyl, propoxyheneicosyl, acid ethyl ester, benzoyl acid propyl ester, benzoyl acid butyl propoxydocosyl, propoxytricosyl, propoxytetracosyl, pro ester, and the like: poxypentacosyl, propoxyhexacosyl, propoxyheptacosyl, (d) all isomers of silylcarbyl radicals including trimethylsi impropoxyoctacosyl, propoxynonacosyl, propoxytriacontyl, lylpropyl, trimethylsilylbutyl, trimethylsilylpentyl, trimeth butoxymethyl, butoxyethyl, butoxypropyl, butoxybutyl, ylsilylhexyl, trimethylsilylheptyl, trimethylsilyloctyl, trim butoxypentyl, butoxyhexyl, butoxyheptyl, butoxyoctyl, ethylsilylnonyl, trimethylsilyldecyl, trimethylsilylundecyl, butoxynonyl, butoxydecyl, butoxyundecyl, butoxydodecyl. trimethylsilyldodecyl, trimethylsilyltridecyl, trimethylsi butoxytridecyl, butoxytetradecyl, butoxypentadecyl, butoxy lyltetradecyl, trimethylsilylpentadecyl, trimethylsilylhexa hexadecyl, butoxyheptadecyl, butoxyoctadecyl, butoxynona decyl, trimethylsilylheptadecyl, trimethylsilyloctadecyl, tri decyl, butoxyeicosyl, butoxyheneicosyl, butoxydocosyl, methylsilylnonadecyl trimethylsilyleicosyl, butoxytricosyl, butoxytetracosyl, butoxypentacosyl, butoxy trimethylsilylheneicosyl, trimethylsilyldocosyl, trimethylsi hexacosyl, butoxyheptacosyl, butoxyoctacosyl, butoxynona lyltricosyl, trimethylsilyltetracosyl, trimethylsilylpentaco cosyl, butoxytriacontyl, dimethylaminopropyl, dimethylami Syl, trimethylsilylhexacosyl, trimethylsilylheptacosyl, trim nobutyl, dimethylaminopentyl, dimethylaminohexyl, ethylsilyloctacosyl, trimethylsilylnonacosyl, dimethylaminoheptyl, dimethylaminooctyl, dimethylami trimethylsilyltriacontyl, dimethylphenylsilylpropyl, dimeth nononyl, dimethylaminodecyl, dimethylaminoundecyl, dim ylphenylsilylbutyl, dimethylphenylsilylpentyl, dimethylphe ethylaminododecyl, dimethylaminotridecyl, dimethylami nylsilylhexyl, dimethylphenylsilylheptyl, dimethylphenylsi notetradecyl dimethylaminopentadecyl lyloctyl, dimethylphenylsilylnonyl, dimethylaminohexadecyl, dimethylaminoheptadecyl, dim dimethylphenylsilyldecyl, dimethylphenylsilylundecyl, dim ethylaminooctadecyl, dimethylaminononadecyl, dimethy ethylphenylsilyldodecyl, dimethylphenylsilyltridecyl, dim laminoeicosyl, dimethylaminoheneicosyl, dimethylamino ethylphenylsilyltetradecyl, dimethylphenylsilylpentadecyl, docosyl, dimethylaminotricosyl, dimethylaminotetracosyl, dimethylphenylsilylhexadecyl, dimethylphenylsilylheptade US 2010/01 13717 A1 May 6, 2010

cyl, dimethylphenylsilyloctadecyl, dimethylphenylsilyl (f) halo substituted phenyl and all isomers of halo substituted nonadecyl, dimethylphenylsilyleicosyl, dimethylphenylsi phenyl (where halo is, independently, fluoro, chloro, and lylheneicosyl, dimethylphenylsilyldocosyl, iodo) including halophenyl, dihalophenyl, trihalophenyl, tet dimethylphenylsilyltricosyl, dimethylphenylsilyltetracosyl, rahalophenyl, and pentahalophenyl; from all isomers of halo dimethylphenylsilylpentacosyl, dimethylphenylsilylhexaco substituted hydrocarbyl substituted phenyl (where halo is, Syl, dimethylphenylsilylheptacosyl, dimethylphenylsilyloc independently, fluoro, chloro, and iodo) including halometh tacosyl, dimethylphenylsilylnonacosyl, dimethylphenylsilyl ylphenyl, dihalomethylphenyl, trihalomethylphenyl, tetraha triacontyl, triethylsilylpropyl, triethylsilylbutyl, lomethylphenyl, haloethlyphenyl, dihaloethylphenyl, triha triethylsilylpentyl, triethylsilylhexyl, triethylsilylheptyl, tri loethylphenyl, tetrahaloethylphenyl, halopropylphenyl, ethylsilyloctyl, triethylsilylnonyl, triethylsilyldecyl, triethyl dihalopropylphenyl, trihalopropylphenyl, tetrahalopropy silylundecyl, triethylsilyldodecyl, triethylsilyltridecyl, trieth lphenyl, halobutylphenyl, dihalobutylphenyl, trihalobu ylsilyltetradecyl, triethylsilylpentadecyl, tylphenyl, tetrahalobutylphenyl, dihalodimethylphenyl, triethylsilylhexadecyl, triethylsilylheptadecyl, triethylsily dihalo(trifluoromethyl)phenyl and the like: loctadecyl, triethylsilylnonadecyl, triethylsilyleicosyl, trieth (g) all isomers of benzyl, and all isomers of hydrocarbyl ylsilylheneicosyl, triethylsilyldocosyl, triethylsilyltricosyl, substituted benzyl including methylbenzyl, dimethylbenzyl, triethylsilyltetracosyl, triethylsilylpentacosyl, triethylsilyl trimethylbenzyl, tetramethylbenzyl, pentamethylbenzyl eth hexacosyl, triethylsilylheptacosyl, triethylsilyloctacosyl, tri ylbenzyl, diethylbenzyl, triethylbenzyl, tetraethylbenzyl, ethylsilylnonacosyl, triethylsilyltriacontyl, 1,1-dimethyl pentaethylbenzyl, propylbenzyl, dipropylbenzyl, tripropyl silolanyl, 1,1-dimethyl-silinanyl, 1,1-dimethyl-silepanyl. benzyl, tetrapropylbenzyl, pentapropylbenzyl butylbenzyl, 1,1-diethyl-silolanyl, 1,1-diethyl-silinanyl, 1,1-diethyl dibutylbenzyl, tributylbenzyl, tetrabutylbenzyl, pentabutyl silepanyl and the like; benzyl, hexylbenzyl, dihexylbenzyl, trihexylbenzyl, tetra (e) phenyl and isomers of methylphenyl, ethylphenyl, propy hexylbenzyl, pentahexylbenzyl, dimethylethylbenzyl, dim lphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphe ethylpropylbenzyl, dimethylbutylbenzyl, nyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dimethylpentylbenzyl, dimethylhexylbenzyl, diethylmethyl dodecylphenyl, tridecylphenyl, tetradecylphenyl, pentade benzyl, diethylpropylbenzyl, diethylbutylbenzyl, diethylpen cylphenyl, hexadecylphenyl, heptadecylphenyl, octade tylbenzyl, diethylhexylbenzyl, dipropylmethylbenzyl, dipro cylphenyl, nonadecylphenyl, eicosylphenyl, heneicosylphe pylethylbenzyl, dipropylbutylbenzyl, dipropylpentylbenzyl, nyl, docosylphenyl, tricosylphenyl, tetracosylphenyl, dipropylhexylbenzyl, dibutylmethylbenzyl, dibutylethylben pentacosylphenyl, hexacosylphenyl, heptacosylphenyl, octa Zyl, dibutylpropylbenzyl, dibutylpentylbenzyl, dibutylhexy cosylphenyl, nonacosylphenyl, triacontylphenyl, dimeth lbenzyl, methylethylbenzyl, methylpropylbenzyl, methylbu ylphenyl, diethylphenyl, dipropylphenyl, dibutylphenyl, tylbenzyl, methylpentylbenzyl, methylhexylbenzyl, dipentylphenyl, dihexylphenyl, diheptylphenyl, dioctylphe ethylpropylbenzyl, ethylbutylbenzyl, ethylpentylbenzyl, eth nyl, dinonylphenyl, didecylphenyl, diundecylphenyl, didode ylhexylbenzyl, propylbutylbenzyl, propylpentylbenzyl, pro cylphenyl, trimethylphenyl, triethylphenyl, tripropylphenyl, pylhexylbenzyl, butylpentylbenzyl, butylhexylbenzyl, trim tributylphenyl, tripentylphenyl, trihexylphenyl, triheptylphe ethylsilylbenzyl, bis(trimethylsilyl)benzyl, nyl, trioctylphenyl, trinonylphenyl, tridecylphenyl, triunde cylphenyl, tridodecylphenyl, tetramethylphenyl, tetraeth trimethylgermylbenzyl, diphenylmethyl and the like: ylphenyl, tetrapropylphenyl, tetrabutylphenyl, (h) trihydrocarbyl-silyl, -germyls, -stannyls and -plumbyls tetrapentylphenyl, tetrahexylphenyl, pentamethylphenyl, including trimethylsilyl, trimethylgermyl, trimethylstannyl, pentaethylphenyl, pentapropylphenyl, pentabutylphenyl, trimethylplumbyl, triethylsilyl, triethylgermyl, dimethyleth ethylmethylphenyl, methylpropylphenyl, butylmethylphe ylsilyl, dimethylethylgermyl, diethylmethylsilyl, diethylm nyl, methylpentylphenyl, hexylmethylphenyl, heptylmeth ethylgermyl, triphenylsilyl, triphenylgermyl, and all isomers ylphenyl, methyloctylphenyl, nonylmethylphenyl, decylm of tripropylsilyl, tripropylgermyl, tributylsilyl, tributylger ethylphenyl, methylundecylphenyl, dodecylmethylphenyl, myl, tris(trifluormethyl)silyl, bis(perfluoromethyl)methylsi dimethylethylphenyl, dimethylpropylphenyl, butyldimeth lyl, and the like: ylphenyl, dimethylpentylphenyl, dimethylhexylphenyl, dim (i) all isomers of hydrocarbyl substituted isomers of polycy ethylheptylphenyl, dimethyloctylphenyl, dimethylnonylphe clic areneyls including pyrenyl, aceanthrylenyl, acenaphthyl nyl, decyldimethylphenyl, dimethylundecylphenyl, ene, acephenanthrylenyl, azulenyl biphenylenyl, chrysenyl, dimethyldodecylphenyl, diethylmethylphenyl, diethylpropy coronenyl, fluoranthenyl, fluorenyl, heptacenyl, heptalenyl, lphenyl, butyldiethylphenyl, diethylpentylphenyl, diethyl heptaphenyl, hexacenyl, hexaphenyl, as-indacenyl, S-indece hexylphenyl, diethylheptylphenyl, diethyloctylphenyl, dieth nyl, indenyl, ovalenyl, pentacenyl, pentalenyl, pentaphenyl, ylnonylphenyl, decyldiethylphenyl, diethylundecylphenyl, perylenyl, phenalenyl, phenanthrenyl, picenyl, pleiadenyl, diethyldodecylphenyl, dipropylmethylphenyl, dipropyleth pyranhrenyl, rubicenyl, naphthacenyl, tetraphenylenyl, tri ylphenyl, butyldipropylphenyl, dipropylpentylphenyl, dipro naphthylenyl, triphenylenyl, hexahelicenyl, naphthyl, anthra pylhexylphenyl, dipropylheptylphenyl, dipropyloctylphenyl, cenyl, dibenzaa,blanthracenyl, indanyl, acenaphthenyl, dipropylnonylphenyl, decyldipropylphenyl, dipropylunde cholanthrenyl, aceanthrenyl, acephenanthrenyl, 1.2.3,4-tet cylphenyl, dipropyldodecylphenyl, dibutylmethylphenyl, rahydronapthalene, fullerenyl, and the like: dibutylethylphenyl, dibutylpropylphenyl, dibutylpentylphe () all isomers of hydrocarbyl Substituted alicyclic, monocy nyl, dibutylhexylphenyl, dibutylheptylphenyl, dibutyloc clic and polycyclic hydrocarbon rings including cyclopropyl. tylphenyl, dibutylnonylphenyl, decyldibutylphenyl, dibuty cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyclohep lundecylphenyl, dibutyldodecylphenyl, vinylphenyl, prop tyl, cyclooctyl, cyclononyl, cyclodecyl cycloundecyl, and enylphenyl, butenylphenyl, methylvinylphenyl, trimethylsi cyclododecyl, dimethylcyclohexyl, norbornyl, norbornenyl, lylphenyl, trimethylgermylphenyl, trifluoromethylphenyl, adamantyl, cubanyl, prismanyl, spiro4.5 decanyl, and the bis(trifluoromethyl)phenyl and the like: like: US 2010/01 13717 A1 May 6, 2010

(k) all isomers of heterocycles and hydrocarbyl substituted yphenyl Zinc chloride, para-fluorophenyl Zinc chloride, meta heterocycles including acridarsinyl, acridinyl, acridophos trifluoromethylphenyl zinc chloride, mesityl Zinc chloride, phinyl, 1 H-acrindolinyl, anthrazinyl, anthyridinyl, arsan 1-naphthyl zinc chloride, 2-thienyl zinc chloride, 2-furyl Zinc thridinyl, arsindolyl, arsindolizinyl, arsinolinyl, arsinoliz chloride, 1-benzothien-2-yl zinc chloride, 1-benzofur-2-yl inyl, benzofuranyl, carbazolyl, B-carbolinyl, chromenyl, Zinc chloride, 5-methyl-2-thienyl Zinc chloride, and 5-me thiochromenyl, cinnolinyl, furanyl (also called furyl), imida thyl-2-furyl Zinc chloride. Zolylindazolyl, indolyl, indolizinyl, isoarsindolyl, isoarsino 0101 While the Negishi coupling reactions are preferred, linyl, isobenzofuranyl, isochromenyl, isothiochromenyl, other palladium catalyzed coupling reactions such as the isoindolyl, isophosphindolyl, isophosphinolinyl, isoquinoli Kumada reaction (using R***MgX*, Ni catalyzed), the nyl, isothiazolyl, isoxazolyl, naphthyridinyl, oxazolyl, peri Suzuki-Miyaura reaction (using NaBPh/LiBR***Ar), the midinyl, phenanthrazinyl, phenanthridinyl, phenanthrolinyl, Stille reaction (using R* Snar), the Heck reaction (using phenazinyl, phosphanthridinyl, phosphindolyl, phosphin HC=CHR***), and the Sonogashira reaction (using dolizinyl, phosphinolizinyl, phthalazinyl, pteridinyl, phtha HC=CR***) may be used, where Ar is an arene, R*** is as loperinyl, purinyl, pyranyl, thiopyranal, pyrazinyl, pyrazolyl, defined above, X* is chlorine, bromine and iodine. pyridazinyl, pyridinyl, pyrindinyl, pyrimidinyl, pyrrolyl pyr 0102 The general protocols for the Negishi reaction using rolizinyl, quinazolinyl, quindolinyl, 1H-quinindolinyl, organozinc transfer-agents, the Kumada reaction using Grig quinolinyl, quinolizinyl, quinoxalinyl, selenophenyl, thebe nard transfer-agents, the Suzuki-Miyaura reaction using nidinyl, thiazolyl, thiophenyl (also called thienyl), tripheno organoborontransfer-reagents (particularly NaBPha, boronic dioxazinyl, triphenodithiazinyl, Xanthenyl, chromanyl, thio acids and their ethers), the Stille reaction using organotin chromanyl, imidazolidinyl, indolinyl, isochromanyl. based transfer-agents, and other cross-coupling reactions are isothiochromanyl, isoindolinyl, morpholinyl, piperazinyl, described in Metal-Catalyzed Cross-Coupling Reactions, Ed. piperidinyl, pyroZolidinyl, pyrrolidinyl, quinuclidinyl, meth by F. Diederich, P. J. Stang, Wiley, 1998 and the references ylthiopehnyl, methylfuranyl, ethylthiopehnyl, ethylfuranyl, cited therein. propylthiopehnyl, propylfuranyl, butylthiopehnyl, butylfura 0103) In addition to the organozinc transfer-agents nyl, pentylthiopehnyl, pentylfuranyl, hexylthiopehnyl, hexy described above, other transfer-agents that can be used in the lfuranyl, dimethylacridarsinyl, dimethylacridinyl, dimethy coupling reactions described herein include but are not lim lacridophosphinyl, dimethyl-1H-acrindolinyl, ited to: dimethylanthrazinyl, dimethylanthyridinyl, dimethylarsan A) boron transfer-agents such as RB(OR*"), RB(OR*"), thridinyl, dimethylarsindolyl, dimethylarsindolizinyl, dim RB, RB(OR*"O), RB(R*"), or NaBR' where R*" is, ethylarsinolinyl, dimethylarsinolizinyl, dibutylbenzofuranyl, independently, hydrogen or hydrocarbyl, and two or more dibutylcarbazolyl, dibutyl-f-carbolinyl, dibutylchromenyl, R*" may join together to form a substituted or unsubstituted dibutylthiochromenyl, butylcinnolinyl, dibutylfuranyl, dim saturated, partially saturated or aromatic cyclic or polycyclic ethylimidazolyl, dimethylindazolyl, dipropylindolyl, dipro ring structure and R' is a substituted or unsubstituted hydro pylindolizinyl, dimethylisoarsindolyl, methylisoarsinolinyl, carbyl, or substituted or unsubstituted fluorocarbyl; dimethylisobenzofuranyl, diphenylisochromenyl, dibutyl B) tin transfer-agents such as R'SnR*", where R*" is a isothiochromenyl, phenylisoindolyl, butylisophosphindolyl, halide, an alkoxide, a carboxylate, or an alkyl, preferably dibutylisophosphinolinyl, dimethylisoquinolinyl, methyl methyl or butyl, and R' is substituted or unsubstituted hydro isothiazolyl, butylisoxazolyl, butylnaphthyridinyl, dimethy carbyl, or substituted or unsubstituted fluorocarbyl; loxazolyl, methylphenylperimidinyl, tetrabutylphenanthrazi C) copper transfer-agents such as R'Cu, where and R' is a nyl, propylphenanthridinyl, dibutylphenanthrolinyl, substituted or unsubstituted hydrocarbyl, or substituted or tetramethylphenazinyl, butylphosphanthridinyl, phenylphos unsubstituted fluorocarbyl, phindolyl, dimethylphosphindolizinyl, methylphosphinoliz D) magnesium transfer-agents such as R'MgX***, where R' inyl, dibutylphthalazinyl, trimethylpteridinyl, methylphtha is substituted or unsubstituted hydrocarbyl, or substituted or loperinyl, dimethylpurinyl, dibutylpyranyl, unsubstituted fluorocarbyl, and X*** is chloride, bromide, an dibutylthiopyranal, trimethylpyrazinyl, phenylpyrazolyl, alkoxide, or a carboxylate; dipropylpyridazinyl, dimethylpyridinyl, methylpropylpy E) aluminum alkyls; rindinyl, triethylpyrimidinyl, dibutylpyrrolyl, diethylpyr F) lithium transfer-agents such as LiR', where R' is substi rolizinyl, dibutylquinazolinyl, dibutylquindolinyl, dibutyl tuted or unsubstituted hydrocarbyl, or substituted or unsub 1H-quinindolinyl, dimethylduinolinyl, propylquinolizinyl, stituted fluorocarbyl; methylduinoxalinyl, methylbutylselenophenyl, methylthebe G) zirconium transfer-agents such as R'ZrCp2X or nidinyl, dimethylthiazolyl, trimethylthiophenyl, dibutylt R'ZrCp, where R' is substituted or unsubstituted hydrocar riphenodioxazinyl, dibutyltriphenodithiazinyl, dibutylxan byl, or substituted or unsubstituted fluorocarbyl, Cp is a thenyl, trimethylchromanyl, dimethylthiochromanyl. cyclopentadienyl group (including an indenyl or fluorenyl dimethylimidazolidinyl, dimethylindolinyl, dibutylisochro group), and X is a halide, an alkoxide or any other monoan manyl, dibutylisothiochromanyl, phenylisoindolinyl, dibu ionic polar group; and tylmorpholinyl, dimethylpiperazinyl, dimethylpiperidinyl, H) organosilanes such as R'SiX,R*', or R', Six, R*, dimethylpyrozolidinyl, dimethylpyrrolidinyl, bipyridyl, where R* is an alkyl or aryl group, R' is a substituted or pyrido 2,1,6-dequinolizinyl, hexamethylcuinuclidinyl, 5.7- unsubstituted hydrocarbyl, or substituted or unsubstituted dioxa-6-phosphadibenzoa,ccycloheptene-6-oxide, 9-Oxa fluorocarbyl, and X is a halide, an alkoxide or any other 10-phosphaphenanthrene-10-oxide and the like. monoanionic polar group, preferably F, and n=0, 1, 2, or 3. 0100 Preferred zinc transfer-agents include: methyl zinc 0104 Specific examples of suitable boron transfer-agents chloride, phenyl Zinc chloride, para-tolyl Zinc chloride, para include but are not limited to methylboronic acid, ethylbo tert-butylphenyl Zinc chloride, biphenyl Zinc chloride, meta ronic acid, n-propylboronic acid, isopropylboronic acid, tolyl Zinc chloride, ortho-tolyl zinc chloride, ortho-methox n-butylboronic acid, sec-butylboronic acid, isobutylboronic US 2010/01 13717 A1 May 6, 2010 20 acid, tert-butylboronic acid, cyclopentylboronic acid, cyclo 1-naphthyl-tri-n-butyltin, 2-naphthyl-tri-n-butyltin, 4-cy hexylboronic acid, benzylboronic acid, 4-methylbenzylbo anophenyl-tri-n-butyltin, 4-carboethoxyphenyl-tri-n-butyl ronic acid, 4-methoxybenzylboronic acid, 4-trifluoromethyl tin, pentafluorophenyl-tri-n-butyltin, phenyltin trichloride, boronic acid, diphenylmethylboronic acid, phenyltin tribromide, phenyltin triiodide, phenyltin trifluo adamantylboronic acid, cyclohexenylboronic acid, isoprope ride, and phenyltin triethoxyde. nylboronic acid, 2-phenylethenylboronic acid, trimethylsilyl 0.108 Particularly preferred tin transfer-agents are 2-thie methylboronic acid, neopentylboronic acid, methoxymethyl nyl-tri-n-butyltin, 3,5-dimethylphenyl-tri-n-butyltin, 2.5- boronic acid, 3-methoxypropylboronic acid, dimethylphenyl-tri-n-butyltin, 3,5-diisopropylphenyl-tri-n- dimethylaminomethylboronic acid, diphenylphosphinom butyltin, 3,5-di-tert-butylphenyl-tri-n-butyltin, and ethylboronic acid, 2-pyridylboronic acid, 4-pyridylboronic 1-naphthyl-tri-n-butyltin. acid, 2-thienylboronic acid, 2-benzothienylboronic acid, 0109 The cross-coupling reactions using organotin trans 2-benzofurylboronic acid, 3-(N-methylindolyl)boronic acid, fer-agent (Stille reaction) require the use of a nucleophilic aid phenylboronic acid, Sodium tetraphenylborate, 4.4.5.5-tet agent (an additive). Non-limiting examples of Such aiding ramethyl-2-phenyl-1,3,2-dioxaborolane, 2-phenyl-1,3,2- agents (additives) to be used include: lithium fluoride, sodium benzodioxaborole, triphenylboron, 2-methylphenylboronic fluoride, potassium fluoride, rubidium fluoride, cesium fluo acid, 3-methylphenylboronic acid, 4-methylphenylboronic ride, tetramethylammonium fluoride, tetraethylammonium acid, 4-tert-butylphenylboronic acid, 2,6-dimethylphenylbo fluoride, tetra-n-butylammonium fluoride, magnesium fluo ronic acid, 2,6-diisopropylphenylboronic acid, 3,5-dimeth ride, calcium fluoride, barium fluoride, aluminium fluoride, ylphenylboronic acid, 2,5-dimethylphenylboronic acid, 3.5- tetramethylphosphonium fluoride, lithium chloride, sodium diisopropylphenylboronic acid, 3,5-di-tert bromide, potassium chloride, rubidium chloride, cesium butylphenylboronic acid, 2-isopropylphenylboronic acid, chloride, tetramethylammonium chloride, tetraethylammo 3-trifluoromethylphenylboronic acid, 4-fluorophenylboronic nium chloride, tetra-n-butylammonium chloride, magnesium acid, 4-methoxyphenylboronic acid, 2-methoxyphenylbo chloride, calcium chloride, barium chloride, aluminium chlo ronic acid, 4-dimethylaminophenylboronic acid, 1-naphthyl ride, tetramethylphosphonium chloride, lithium hydroxide, boronic acid, 2-naphthylboronic acid, 4-cyanophenylboronic Sodium hydroxide, potassium hydroxide, rubidium hydrox acid, 4-carboethoxyphenylboronic acid, and pentafluorophe ide, cesium hydroxide, tetramethylammonium hydroxide, nylboronic acid. tetraethylammonium hydroxide, tetra-n-butylammonium 0105 Particularly preferred boron transfer-agents are hydroxide, magnesium hydroxide, calcium hydroxide, 2-thienylboronic acid, 3,5-dimethylphenylboronic acid, 2.5- barium hydroxide, aluminium hydroxide, tetramethylphos dimethylphenylboronic acid, 3,5-diisopropylphenylboronic phonium hydroxide, lithium methoxide, sodium methoxide, acid, 3,5-di-tert-butylphenylboronic acid, and 1-naphthylbo potassium methoxide, rubidium methoxide, cesium methox ronic acid. ide, magnesium methoxide, calcium methoxide, barium 0106 The cross-coupling reactions using organoboron methoxide, aluminium methoxide, Sodium ethoxide, Sodium transfer-agents (Suzuki-Miyaura reaction) require a base (an n-propoxide, Sodium isopropoxide, Sodium n-butoxide, additive) in addition to NaBPh. Non-limiting examples of Sodium isobutoxide, sodium sec-butoxide, Sodium phenox bases (additives) to be used include: potassium carbonate, ide. Sodium carbonate, lithium carbonate, cesium carbonate, 0110 Specific examples of suitable copper transfer-agents rubidium carbonate, lithium hydroxide, sodium hydroxide, include but are not limited to ethynylcopper, prop-1-ynylcop potassium hydroxide, Sodium triphosphate, potassium triph per, but-1-ynylcopper, (3-methylbut-1-ynyl)copper, (3.3- osphate, Sodium hydrocarbonate, calcium carbonate, calcium dimethylbut-1-ynyl)copper, (2-phenylethynyl)copper, (2-(3. oxide, barioum carbonate, barium oxide, aluminium carbon 5-dimethylphenyl)ethynyl)copper, (2-(2,5-dimethylphenyl) ate, aluminium oxide, yttrium carbonate, yttrium oxide, ethynyl)copper, (2-(3,5-di-iso-propylphenyl)ethynyl)copper, cerium carbonate, cerium oxide, barium hydroxide, calcium (2-(3,5-di-tert-butyl-phenyl)ethynyl)copper, (2-mesity lethy hydroxide, yttrium hydroxide, cerium hydroxide, aluminium nyl)copper, and (2-(naphth-1-yl)ethynyl)copper. hydroxide, Sodium methylate, sodium ethylate, Sodium iso 0111 Specific examples of suitable magnesium transfer propylate, Sodium n-butoxide, sodium tert-butoxide, lithium agents include but are not limited to methylmagnesium chlo ethylate, potassium ethylate. ride, methylmagnesium bromide, methylmagnesium iodide, 0107 Specific examples of suitable tin transfer-agents dimethylmagnesium, ethylmagnesium bromide, n-propyl include but are not limited to tetramethyltin, teraethyltin, magnesium chloride, isopropylmagnesium chloride, n-butyl tetracyclohexyltin, 2-pyridyl-tri-n-butyltin, 4-pyridyl-tri-n- magnesium chloride, sec-butylmagnesium chloride, isobu butyltin, 2-thienyl-tri-n-butyltin, 2-benzothienyl-tri-n-butyl tylmagnesium chloride, tert-butylmagnesium chloride, tin, 2-benzofuryl-tri-n-butyltin, 3-(N-methylindolyl)-tri-n- cyclopentylmagnesium chloride, cyclohexylmagnesium butyltin, phenyl-tri-n-butyltin, phenyltrimethyltin, chloride, benzylmagnesium chloride, 4-methylbenzylmag phenyltriethyltin, phenyltriisopropyltin, phenyltriisobutyltin, nesium chloride, 4-methoxybenzylmagnesium chloride, phenyltricyclohexyltin, tetraphenyltin, 2-methylphenyl-tri 4-trifluoromethylmagnesium chloride, diphenylmethylmag n-butyltin, 3-methylphenyl-tri-n-butyltin, 4-methylphenyl nesium bromide, adamantylmagnesum bromide, cyclohex tri-n-butyltin, 4-tert-butylphenyl-tri-n-butyltin, 2,6-dimeth enylmagnesium chloride, isopropenylmagnesium chloride, ylphenyl-tri-n-butyltin, 2,6-diisopropylphenyl-tri-n-butyltin, 2-phenylethenylmagnesium bromide, trimethylsilylmethyl 3,5-dimethylphenyl-tri-n-butyltin, 2,5-dimethylphenyl-tri-n- magnesium chloride, neopentylmagnesium chloride, meth butyltin, 3,5-diisopropylphenyl-tri-n-butyltin, 3,5-di-tert-bu oxymethylmagnesium chloride, 3-methoxypropylmagne tylphenyl-tri-n-butyltin, 2-isopropylphenyl-tri-n-butyltin, sium chloride, dimethylaminomethylmagnesium chloride, 3-trifluoromethylphenyl-tri-n-butyltin, 4-fluorophenyl-tri-n- diphenylphosphinomethylmagnesium chloride, 2-pyridyl butyltin, 4-methoxyphenyl-tri-n-butyltin, 2-methoxyphenyl magnesium bromide, 4-pyridylmagnesium chloride, 2-thie tri-n-butyltin, 4-dimethylaminophenyl-tri-n-butyltin, nylmagnesium bromide, 2-benzothienylmagne sium bro US 2010/01 13717 A1 May 6, 2010 mide, 2-benzo furylmagnesium chloride, 3-(N- sec-butyllithium, isobutyllithium, tert-butyllithium, cyclo methylindolyl)magnesium bromide, phenylmagnesium pentyllithium, cyclohexyllithium, benzyllithium, 4-methyl bromide, 2-methylphenylmagnesium bromide, 3-methylphe benzyllithium, 4-methoxybenzyllithium, 4-trifluoromethyl nylmagnesium bromide, 4-methylphenylmagnesium bro lithium, diphenylmethyllithium, adamantyllithium, mide, 4-tert-butylphenylmagnesium bromide, 2,6-dimeth cyclohexenyllithium, isopropenyllithium, 2-phenylethenyl ylphenylmagnesium bromide, 2,6- lithium, trimethylsilylmethyllithium, neopentyllithium, diisopropylphenylmagnesium bromide, 3,5- methoxymethyllithium, 3-methoxypropyllithium, dimethy dimethylphenylmagnesium chloride, 2.5- laminomethyllithium, diphenylphosphinomethyllithium, dimethylphenylmagnesium chloride, 3,5- 2-pyridyllithium, 4-pyridyllithium, 2-thienyllithium, 2-ben diisopropylphenylmagnesium chloride, 3,5-di-tert Zothienyllithium, 2-benzofuryllithium, 3-(N-methylindolyl) butylphenylmagnesium chloride, lithium, phenyllithium, 2-methylphenyllithium, 3-meth 2-isopropylphenylmagnesium chloride, 3-trifluorometh ylphenyllithium, 4-methylphenyllithium, 4-tert ylphenylmagnesium chloride, 4-fluorophenylmagnesium butylphenylithium, 2,6-dimethylphenyllithium, 2,6- chloride, 4-methoxyphenylmagnesium chloride, 2-methox diisopropylphenyllithium, 3,5-dimethylphenyllithium, 2.5- yphenylmagnesium chloride, 4-dimethylaminophenylmag dimethylphenylithium, 3,5-diisopropylphenyllithium, 3.5- nesium chloride, 1-naphthylmagnesium chloride, 2-naphth di-tert-butylphenyllithium, 2-isopropylphenyllithium, ylmagnesium chloride, and pentafluorophenylmagnesium 3-trifluoromethylphenyllithium, 4-fluorophenyllithium, bromide. 4-methoxyphenyllithium, 2-methoxyphenyllithium, 4-dim 0112 Particularly preferred magnesium transfer-agents ethylaminophenyllithium, 1-naphthyllithium, 2-naphthyl are cyclopentylmagnesium chloride, cyclohexylmagnesium lithium, and pentafluorophenylithium. chloride, 2-thienylmagnesium bromide, 3,5-dimethylphenyl 0115 Particularly preferred lithium transfer-agents are magnesium chloride, 2,5-dimethylphenylmagnesium chlo cyclopentyllithium, cyclohexyllithium, 2-thienyllithium, ride, 3,5-diisopropylphenylmagnesium chloride, 3.5-di-tert 3,5-dimethylphenyllithium, 2,5-dimethylphenyllithium, 3.5- butylphenylmagnesium chloride, and 1-naphthylmagnesium diisopropylphenyllithium, 3,5-di-tert-butylphenyllithium, chloride. and 1-naphthyllithium. 0113 Specific examples of suitable aluminum alkyl trans 0116 Specific examples of suitable zirconium transfer fer-agents include but are not limited to (prop-1-enyl)diisobu agents includebut are not limited to (prop-1-enyl)dicyclopen tylaluminum, (but-1-enyl)disobutylaluminum, (pent-1-enyl) tadienylzirconium chloride, (but-1-enyl)dicyclopentadi disobutylaluminum, (hex-1-enyl)diisobutylaluminum, enylzirconium chloride, (pent-1-enyl) (3-methylbut-1-enyl)diisobutylaluminum, (3,3-dimethylbut dicyclopentadienylzirconium chloride, (hex-1-enyl) 1-enyl)diisobutylaluminum, (4-methylpent-1-enyl)diisobu dicyclopentadienylzirconium chloride, (3-methylbut-1-enyl) tylaluminum, (3-methylpent-1-enyl)disobutylaluminum, dicyclopentadienylzirconium chloride, (3.3-dimethylbut-1- (styryl)diisobutylaluminum, (3,5-dimethylstyryl)diisobuty enyl)dicyclopentadienylzirconium chloride, (4-methylpent laluminum, (2,5-dimethylstyryl)diisobutylaluminum, (3.5- 1-enyl)dicyclopentadienylzirconium chloride, di-tert-butylstyryl)diisobutylaluminum, (2,4,6-trimethyl (3-methylpent-1-enyl)dicyclopentadienylzirconium chlo styryl)diisobutylaluminum, (2-(naphth-1-yl) vinyl) ride, (styryl)dicyclopentadienylzirconium chloride, (3.5- disobutylaluminum, (but-2-en-2-yl)disobutylaluminum, dimethylstyryl)dicyclopentadienylzirconium chloride, (2.5- (pent-2-en-2-yl)diisobutylaluminum, (hex-2-en-2-yl)gli dimethylstyryl)dicyclopentadienylzirconium chloride, (3.5- isobutylaluminum, (hept-2-en-2-yl)diisobutylaluminum, di-tert-butylstyryl)dicyclopentadienylzirconium chloride, (4-methylpent-2-en-2-yl)diisobutylaluminum, (4,4-dimeth (2,4,6-trimethylstyryl)dicyclopentadienylzirconium chlo ylpent-2-en-2-yl)gliisobutylaluminum, (5-methylhex-1-enyl) ride, (2-(naphth-1-yl)Vinyl)dicyclopentadienylzirconium disobutylaluminum, (4-methylhex-2-en-2-yl)diisobutylalu chloride, (but-2-en-2-yl)dicyclopentadienylzirconium chlo minum, (1-phenyl-1-prop-2-enyl)diisobutylaluminum, (1-(3. ride, (pent-2-en-2-yl)clicyclopentadienylzirconium chloride, 5-dimethylphenyl)-1-prop-2-enyl)diisobutylaluminum, (1- (hex-2-en-2-yl)dicyclopentadienylzirconium chloride, (hept (2,5-dimethylphenyl)-1-prop-2-enyl)diisobutylaluminum, 2-en-2-yl)glicyclopentadienylzirconium chloride, (4-methyl (1-(3,5-di-tert-butyl-phenyl)-1-prop-2-enyl)diisobutylalu pent-2-en-2-yl)clicyclopentadienylzirconium chloride, (4.4- minum, (1-(2,4,6-trimethylphenyl)-1-prop-2-enyl)diisobu dimethylpent-2-en-2-yl)dicyclopentadienylzirconium tylaluminum, (1-(naphth-1-yl)prop-1-en-2-yl)diisobutylalu chloride, (5-methylhex-1-enyl)dicyclopentadienylzirconium minum, (2-methylprop-1-enyl)diisobutylaluminum, chloride, (4-methylhex-2-en-2-yl)dicyclopentadienylzirco (2-methylbut-1-enyl)diisobutylaluminum, (2-methylpent-1- nium chloride, (1-phenyl-1-prop-2-enyl)dicyclopentadi enyl)diisobutylaluminum, (2-methylhex-1-enyl)diisobutyla enylzirconium chloride, (1-(3,5-dimethylphenyl)-1-prop-2- luminum, (2,3-dimethylbut-1-enyl)diisobutylaluminum, enyl)dicyclopentadienylzirconium chloride, (1-(2,5- (2,3,3-trimethylbut-1-enyl)diisobutylaluminum, (2,4-dim dimethylphenyl)-1-prop-2-enyl) ethylpent-1-enyl)diisobutylaluminum, (2,3-dimethylpent-1- dicyclopentadienylzirconium chloride, (1-(3,5-di-tert-butyl enyl)diisobutylaluminum, (2-phenylprop-1-enyl)diisobuty phenyl)-1-prop-2-enyl)dicyclopentadienylzirconium laluminum, (2-(3,5-dimethylphenyl)prop-1-enyl) chloride, (1-(2,4,6-trimethylphenyl)-1-prop-2-enyl)dicyclo disobutylaluminum, (2-(2,5-dimethylphenyl)prop-1-enyl) pentadienylzirconium chloride, (1-(naphth-1-yl)prop-1-en disobutylaluminum, (2-(3,5-di-tert-butylphenyl)prop-1- 2-yl)dicyclopentadienylzirconium chloride, (2-methylprop enyl)diisobutylaluminum, (2-(2,4,6-trimethylphenyl)prop 1-enyl)dicyclopentadienylzirconium chloride, (2-methylbut 1-enyl)diisobutylaluminum, and (2-(naphth-1-yl)prop-1- 1-enyl)dicyclopentadienylzirconium chloride, enyl)diisobutylaluminum. (2-methylpent-1-enyl)dicyclopentadienylzirconium chlo 0114 Specific examples of suitable lithium transfer ride, (2-methylhex-1-enyl)dicyclopentadienylzirconium agents include but are not limited to methyllithium, ethyl chloride, (2,3-dimethylbut-1-enyl)dicyclopentadienylzirco lithium, n-propyllithium, isopropyllithium, n-butyllithium, nium chloride, (2,3,3-trimethylbut-1-enyl)dicyclopentadi US 2010/01 13717 A1 May 6, 2010 22 enylzirconium chloride, (2,4-dimethylpent-1-enyl)dicyclo luorosilane, 4-trifluoromethyltrifluorosilane, pentadienylzirconium chloride, (2,3-dimethylpent-1-enyl) diphenylmethyltrifluorosilane, adamantyltrifluorosilane, dicyclopentadienylzirconium chloride, (2-phenylprop-1- cyclohexenyltrifluorosilane, isopropenyltrifluorosilane, enyl)dicyclopentadienylzirconium chloride, (2-(3.5- 2-phenylethenyltrifluorosilane, trimethylsilylmethyltrifluo dimethylphenyl)prop-1-enyl)dicyclopentadienylzirconium rosilane, neopentyltrifluorosilane, methoxymethyltrifluo chloride, (2-(2,5-dimethylphenyl)prop-1-enyl)dicyclopenta rosilane, and 3-methoxypropyltrifluorosilane. dienylzirconium chloride, (2-(3,5-di-tert-butylphenyl)prop 0118 Aliphatic, heteroaliphatic, aromatic, heteroaro 1-enyl)dicyclopentadienylzirconium chloride, (2-(2,4,6-tri matic, alkenyl, and heteroalkenyl organometallic compounds methylphenyl)prop-1-enyl)dicyclopentadienylzirconium useful as the transfer-agents in the present coupling reactions chloride, and (2-(naphth-1-yl)prop-1-enyl)dicyclopentadi are obtainable in a simple manner by standard methods of the enylzirconium chloride. prior art or can be purchased commercially. The synthesis of 0117 Specific examples of suitable organosilane transfer organozinc transfer-agents, of importance in Negishi reac agents include but are not limited to phenyldimethylfluorosi tions, is described, for example, in Organozinc Reagents, Ed. lane, 2-methylphenyldimethylfluorosilane, 3-methylphe by P. Knochel, P. Jones, Oxford University Press, 1999. The nyldimethylfluorosilane, synthesis of boronic acid transfer-agents, of importance in 4-methylphenyldimethylfluorosilane, 4-tert-butylphe Suzuki-Miyaura reactions, is described, for example, in nyldimethylfluorosilane, 2,6-dimethylphenyldimethylfluo Organic Synthesis, Collective Volume IV, Wiley, 1963. The rosilane, 2,6-diisopropylphenyldimethylfluorosilane, 3.5- synthesis of organotin transfer-agents, of importance in Stille dimethylphenyldimethylfluorosilane, 2.5- reactions, is described, for example, in V. Farina, V. Krishna dimethylphenyldimethylfluoro silane, 3,5- murthy, W.J. Scott, The Stille Reaction, Wiley, 1998 and the diisopropylphenyldimethylfluoro silane, 3,5-di-tert references cited therein. The synthesis of other organometal butylphenyldimethylfluorosilane, lic transfer-agents of the formula (III) involves standard 2-isopropylphenyldimethylfluorosilane, 3-trifluorometh methods of organometallic chemistry and is described, for ylphenyldimethylfluorosilane, 4-fluorophenyldimethylfluo example, in Organometallics in Synthesis, Ed. By M. Schlo rosilane, 4-methoxyphenyldimethylfluorosilane, 2-methox sser, and in J. March, Advanced Organic Chemistry, 4" Edi yphenyldimethylfluorosilane, tion, 1992 and the references cited therein. 4-dimethylaminophenyldimethylfluorosilane, 1-naphth 0119 Catalysts for suitable for use in the present coupling yldimethylfluorosilane, 2-naphthyldimethylfluorosilane, reactions include but are not limited to (a) nickel complexes pentafluorophenyldimethylfluorosilane, phenylethyldifluo such as nickel(II) chloride, nickel(II) bromide, (2,2'-bipyri rosilane, 2-methylphenylethyldifluorosilane, 3-methylphe dine)dibromonickel(II), dichlorobis(triphenylphosphine) nylethyldifluorosilane, 4-methylphenylethyldifluorosilane, nickel(II), dibromobis(triphenylphosphine)nickel(II), 4-tert-butylphenylethyldifluorosilane, 2,6-dimethylphenyl dichloro1,2-bis(diphenylphosphino) ethane nickel(II), ethyldifluorosilane, 2,6-diisopropylphenylethyldifluo dichloro1,3-bis(diphenylphosphino)propanelnickel(II), rosilane, 3,5-dimethylphenylethyldifluorosilane, 2,5-dimeth dichloro1,1'-bis(diphenylphosphino)ferrocene nickel(II), ylphenylethyldifluoro silane, 3,5- bis(1,5-cyclooctadiene) nickel(O), tetrakis(triphenylphos diisopropylphenylethyldifluoro silane, 3,5-di-tert phine)nickel(0), and nickel(II) acetylacetonato; (b) palla butylphenylethyldifluorosilane, dium-phoshine complexes such as bis(tri(tert-butyl)phos 2-isopropylphenylethyldifluorosilane, 3-trifluoromethylphe phine)palladium, bis(tricyclohexylphosphine)palladium, bis nylethyldifluorosilane, 4-fluorophenylethyldifluorosilane, (tri(iso-propyl)phosphine)palladium, dichlorobis(tri(iso 4-methoxyphenylethyldifluorosilane, 2-methoxyphenyleth propyl)phosphine)palladium(II), dichlorobis(tri(o-tolyl) yldifluorosilane, 4-dimethylaminophenylethyldif phoshine)palladium(II), trans-dichlorobis luorosilane, 1-naphthylethyldifluorosilane, 2-naphthyleth (tricyclohexylphosphine) palladium(II), trans-dichlorobis yldifluorosilane, pentafluorophenylethyldifluorosilane, (triphenylphosphine)palladium(II), trans-dichlorobis(tri-o- phenylpropyldifluorosilane, 2-methylphenylpropyldifluo tolylphosphine)palladium(II), tetrakis(triphenylphosphine) rosilane, 3-methylphenylpropyldifluorosilane, 4-methylphe palladium(0), tetrakis(tri(o-tolyl)phosphine)palladium(0), nylpropyldifluorosilane, 4-tert-butylphenylpropyldifluorosi dichloro1,1'-bis(diphenylphosphino)ferrocenepalladium lane, 2,6-dimethylphenylpropyldifluorosilane, 2,6- (II), dichloro 1,2-bis(diphenylphosphino)ethane)palladium diisopropylphenylpropyldifluorosilane, 3,5- (II), dichloro1,3-bis(diphenylphosphino)propanepalla dimethylphenylpropyldifluorosilane, 2.5- dium(II), dichloro 1,4-bis(diphenylphosphino)butane dimethylphenylpropyldifluoro silane, 3,5- palladium(II), dichlorobis(triphenylphosphine)palladium(II) diisopropylphenylpropyldifluoro silane, 3,5-di-tert polymer bound or tetrakis(triphenylphosphine)palladium(0) butylphenylpropyldifluorosilane, polymer bound (both are available from Aldrich Chemical 2-isopropylphenylpropyldifluorosilane, 3-trifluorometh Company where the polymer is a divinylbenzene crosslinked ylphenylpropyldifluorosilane, 4-fluorophenylpropyldifluo polystyrene), benzylbis(triphenylphosphine) palladium(II) rosilane, 4-methoxyphenylpropyldifluorosilane, 2-methox chloride, trans-di(L-acetato)biso-(di(o-tolyl)phosphino) yphenylpropyldifluorosilane, benzyldipalladium(II), and trans-di(t-acetato)biso-(di 4-dimethylaminophenylpropyldifluorosilane, 1-naphthyl mesityl-phosphino) benzyldipalladium(II); (c) palladium propyldifluorosilane, 2-naphthylpropyldifluorosilane, pen compounds such as palladium(II) acetate, palladium(0) tafluorophenylpropyldifluorosilane, methyltrifluorosilane, dibenzylideneacetone, palladium(II) chloride, palladium(II) ethyltrifluorosilane, n-propyltrifluorosilane, isopropyltrif bromide, palladium(II) iodide, palladium(II) acetylaceto luorosilane, n-butyltrifluorosilane, sec-butyltrifluorosilane, nate, allylpalladium chloride dimer, bis(2-methylallyl)palla isobutyltrifluorosilane, tert-butyltrifluorosilane, cyclopentyl dium chloride dimer, crotylpalladium chloride dimer, palla trifluorosilane, cyclohexyltrifluorosilane, benzyltrifluorosi dium(II) trifluoroacetate, dichloro(1,5-cyclo octadiene) lane, 4-methylbenzyltrifluorosilane, 4-methoxybenzyltrif palladium(II), dichlorobis(benzonitrile)palladium(II), US 2010/01 13717 A1 May 6, 2010 dichlorobis(acetonitrile)palladium(II), and tris(dibenzylide hydrocarbyl or fluorocarbyl, and phosphine like reagents. neacetone)dipalladium(0); (d) copper catalysts such as cop Non-limiting examples of phosphine (A through G and N) per(I) cyanide, copper(I) chloride, copper(I) iodide, copper(I) and phosphine like reagents (H through M) are listed below. trifluoroacetate, copper(II) fluoride, copper(II) chloride, and copper(II) iodide; (e) silver catalysts such as silver(I) iodide: and (f) cobalt catalysts such as cobalt(II) bromide, and cobalt (II) acetylacetonate. A

0120 In most cases it is sufficient to use the particularly P preferred catalyst Pd(OAc)(OAc—OCCH) in combina tBu1 n Bu tion with a phosphine or a phosphine-like ligand Such as ligands A-N, or Pd(PBus), in an amount of 0.000001 to 5.0 B mol % Pd, preferably 0.01 to 3.0 mol% Pd and most prefer ably about 1.0 to 2.5 mol % Pd, in each case based on the metallocene starting material. Most preferably, the coupling Bu catalyst is 2.5 mol% Pd or less, relative to the transition metal starting material. Analogously, in most cases it is sufficient to Pn, use the particularly preferred coupling-catalyst NiCl2(dppp) Bu (dppp=1,3-bis(diphenylphosphino)propane) or NiCl (PPh), (Ph-phenyl) in an amount of 0.01 to 5 mol % Ni, preferably 1 to 3 mol % Ni and most preferably about 2 mol C % Ni, in each case relative to the transition metal (typically a metallocene) starting material. 0121 The molar ratio of transfer-agent to X* is preferably N Bu 1:1 to 4:1 and is dependent on the coupling reaction being used. For Negishi and Suzuki-Miyaura reactions, the pre P n ferred molar ratio of transfer-agent to X* is from 1:1 to 2:1, preferably 1.0:1 to 1.5:1; more preferably 1.2:1 to 1.35:1 For O Bu the Heck reaction, the preferred molar ratio of transfer-agent to X* is 1:1 to 3:1, preferably 1.5:1 to 2.5:1, most preferably, D 1.5:1 to 2:1. For all coupling reactions lower than stoichio metric ratios of transfer-agent to X* can be used, however, this is at the expense of lowering the yield of the final product. X* of the transition metal compound (sometimes referred to as the first compound) can be selected from Cl, Br, I, OTs or OTf. In general, reactivity of X* decreases in the order of DBrd-OTf>CDOTs. While it is possible for X of the transi tion metal compound to undergo an exchange with ions gen P erated in the reaction such as LiBr, ZnBrC1, etc., the cross coupling reaction on the transition metal ligand (ligand-X) still works to form the substituted transition metal ligand (ligand-R***). Some choices can be made to limit or prevent E this side reaction. Typically, if X* is more reactive than X, then the side reaction is reduced, or entirely eliminated. If X* p. is the same as X, then the side reaction, even if it occurs, is PN inconsequential. For example, The cross-coupling reaction of Bu (Cp)(Cp-X*)ZrC1, where X* is Bror C1 with R***ZnC1, will produce (Cp)(Cp-R***)ZrC1. Additionally, less harsh reac Fe tion conditions such are performing the Negishi reaction at room temperature and for shorter reaction times (hours vs. () - days) will lower or eliminate this type of side reaction. K 0122 Useful additives include but are not limited to (a) Bu bases Such as Sodium methoxide, Sodium ethoxide, potassium F tert-butoxide, lithium hydroxide, sodium hydroxide, potas sium hydroxide, barium hydroxide, thallium hydroxide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl) amide, potassium bis(trimethylsilyl)amide, triethylamine, ethyldiisopropylamine, benzyldimethylamine, propylamine, O butylamine, diethylamine, diisopropylamine, sodium acetate, potassium acetate, sodium carbonate, potassium car bonate, cesium carbonate, calcium carbonate, thallium car bonate, Sodium bicarbonate, potassium phosphate, pyridine, N-methylpyrrolidinone, piperidine, 2.2.5.5,6-pentamethylpi peridine, pyrrolidine, diaza2.2.2 bicylcooctane, and any of the phosphines R'R"R"P, where each R', R", and R" is a US 2010/01 13717 A1 May 6, 2010 24

(b) salts such as lithium chloride, Sodium chloride, potassium -continued chloride, Sodium bromide, sodium iodide, potassium fluo ride, cesium fluoride, tetrabutylammonium fluoride, tetrabu tylammonium chloride, tetrabutylammonium bromide, tetra ethylammonium chloride, tetrapropylammonium bromide, benzyltriethylammonium bromide, benzyltrioctylammo nium chloride, tris(diethylamino)sulfonium difluoro(trim ethyl)silicate, nickel(II) bromide, silver(I) carbonate, silver (I) phosphate, silver(I) nitrate, silver(I) acetate, silver trifluoroacetate, silver(I) oxide, thallium(I) carbonate, thal lium(I) acetate, zinc.(II) chloride, zinc.(II) bromide, copper(I) Pro cyanide, copper(I) chloride, copper(I) bromide, copper(I) iodide, copper(II) chloride, and copper(II) oxide; and (c) other reagents such as chlorotrimethylsilane, 18-crown-6. triphenylarsine, and triphenylantimony. I0123 Suitable solvents for the metal-catalyzed cross-cou (b. O pling of the invention include, for example, aliphatic ethers such as diethyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane and dimethoxyethane, aliphatic hydrocarbons such as pentane, hexane and the like, aromatic H hydrocarbons such as benzene, toluene, Xylenes and the like. iPr iPr In many cases, other solvents can be used. Such as dimethyl formamide, water, acetone and the like. Mixtures of various Solvents in various mixing ratios can also be used according N N1 N to the present invention to match the solubility of the starting GE) materials and end products to the reaction conditions in an optimal fashion. It should be noted that protic solvents such as iPr iP. water, alcohols and their mixtures with aprotic solvents can CO be also be used, but are typically used only when the starting w K materials, reagents, catalysts and additives cannot be decom posed (by hydrolysis) in Such solvents. For example, the H H cross-coupling reaction of Br-substituted CpTi(OR), which can be definitely performed in the alcohol, ROH, where R is a alkane radical. s L 0.124 Those of ordinary skill in the art will choose sol vents or solvent mixtures appropriate to the specific Substitu HN NH2 tion pattern of the starting compounds, the catalysts and M reagents used by means of simple tests or on the basis of known solubilities and solvent properties. 0.125. In preferred embodiments of the process of the present invention, the metallocene starting material together with a sufficient amount of solvent are placed in the reaction o N N o H H vessel under an inert atmosphere. The coupling-catalyst, an N optional ligand and an optional base or nucleophilic aid agent are subsequently added followed by the addition of a solution of the transfer-agent in a suitable solvent at room or lower (-78°C. to +10°C.) temperatures. The cross-coupling reac PCy2 tion can be carried out by vigorous stirring at room or elevated temperatures (10° C. to 180°C., preferably 20° C. to 100° C.) iPrC) OiPr depending on the reaction under study, the reagents and the coupling-catalyst used. Addition of the metallocene starting material, coupling-catalyst and other additives can be per formed in different orders. Those of ordinary skill in the art will choose an appropriate procedure depending on the reac Additionally, polymeric bound or polymer Supported phos tivity and substitution of the individual reagents. phines may be used. Examples of commercially available polymeric bound phosphines include poly(ethylene glycol) 0.126 Suitable halogen substituted metallocene com triphenylphosphine; and dicyclohexylphenylphosphine, pounds that can be subjected to the cross-coupling reactions polymer-bound; (4-hydroxyphenyl)diphenylphosphine, of the invention include, but are not limited to: polymer-bound; triphenylphosphine, polymer-supported; I0127 (m-cyclopentadienyl)(m-4-bromo-2-methylinde R-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthalene, nyl)Zirconium dichloride, polymer-bound: S-(-)-2,2'-bis(diphenylphosphino)-1,1'-bi I0128 (m-3-tert-butylcyclopentadienyl)(m-4-bromo-2- naphthalene, polymer-bound (all available from Aldrich methylindenyl)Zirconium dichloride, Chemical Company where the polymer-bound or polymer I0129 (m-3-trimethylsilylcyclopentadienyl)(m-4- Supported is a divinylbenzene crosslinked polystyrene). bromo-2-methylindenyl)Zirconium dichloride,

US 2010/01 13717 A1 May 6, 2010 26

(0193 (m-cyclopentadienyl)(m-4-bromocyclopentab (0225 (m-cyclopentadienyl)(m-3-bromo-6H-indeno2, pyridyl)Zirconium dichloride, 1-b1benzothienyl)Zirconium dichloride, (0194 (m-cyclopentadienyl)(m-4-bromocyclopentab 10226 (m-cyclopentadienyl)(m-2-bromo-5-methylin phosphoranyl)Zirconium dichloride, deno1,2-bindolyl)Zirconium dichloride, (0195 (m-cyclopentadienyl)(m-2,6-dibromo-1-dimethy 10227 (m-cyclopentadienyl)(m-8-bromo-5-methylin lamino-1-boratobenzene)Zirconium dichloride, deno1,2-bindolyl)Zirconium dichloride, (0196) (m-cyclopentadienyl)(m-4-bromo-3-dimethy (0228 (m-cyclopentadienyl)(m-8-bromo-5-methylin lamini-1,3-thiaborindenyl)Zirconium dichloride, deno.2.1-bindolyl)Zirconium dichloride, (0197) (m-cyclopentadienyl)(m-4-bromo-3a,7a 0229 (m-cyclopentadienyl)(m-3-bromo-5-methylin azaborindenyl)Zirconium dichloride, deno.2.1-bindolyl)Zirconium dichloride, (0198 (m-cyclopentadienyl)(m-7-bromo-2-dimethy 0230 (mi-pentamethylcyclopentadienyl)(m-2-5-bro lamino-1,2-benzothiaboralide)Zirconium dichloride, monaphth-1-ylindenyl)Zirconium dichloride, (0199 (m-cyclopentadienyl)(m-3-bromo-2-dimethy 0231 (mi-pentamethylcyclopentadienyl)(m-2-7-fluo lamino-1,2-thiaborollide)Zirconium dichloride, robenzothien-2-ylindenyl)Zirconium dichloride, (0200 (m-cyclopentadienyl)(m-2-(4-bromophenyl-in 0232 (m-pentamethylcyclopentadienyl)(m-2-[2-chlo denyl)Zirconium dichloride, robenzothien-4-ylindenyl)Zirconium dichloride, 0201 (m-cyclopentadienyl)(m-2-4-chlorophenyl-in 0233 (m-4-bromo-2-methylindenyl)zirconium trichlo denyl)Zirconium dichloride, ride, (0202) (m-cyclopentadienyl)(m-2-4-iodophenyl-inde 0234 (m-2-bromoindenyl)Zirconium trichloride, nyl)Zirconium dichloride, 0235 (m-4-bromo-2-methylindenyl)zirconium trichlo (0203 (m-cyclopentadienyl)(m-2-4-fluorophenyl-inde ride, nyl)Zirconium dichloride, 0236 (m-4-chloro-2-methylindenyl)zirconium trichlo 0204 (m-cyclopentadienyl)(m-2-5-bromothien-2-yl)- ride, indenyl)Zirconium dichloride, 0237 (m-4-fluoro-2-methylindenyl)zirconium trichlo 0205 (m-cyclopentadienyl)(m-2-4-bromopyridin-2- ride, yl)-indenyl)Zirconium dichloride, 0238 (m-4-iodo-2-methylindenyl)zirconium trichloride, (0206 (m-cyclopentadienyl)(m-2-bromoindenyl)zirco 0239 (m-4-bromo-2-methylindenyl)zirconium tribro nium dichloride, mide, 0207 (m-cyclopentadienyl)(m-3-bromoindenyl)zirco (0240 (m-4-bromo-2-methylindenyl)zirconium triiodide, nium dichloride, 0241 (m-4-bromo-2-methylindenyl)Zirconium trifluo (0208 (m-cyclopentadienyl)(m-2-chloroindenyl)zirco ride, nium dichloride, 0242 (m-4-bromo-2-methylindenyl)Zirconium trihy (0209 (m-cyclopentadienyl)(m-2-bromofluorenyl)zirco dride, nium dichloride, 10243 (m-4-bromo-2-methylindenyl)trimethylzirconium, 0210 (m-cyclopentadienyl)(m-2-todofluorenyl)Zirco 0244 (m-4-bromo-2-methylindenyl)triphenylzirconium, nium dichloride, (0245 (m-4-bromo-2-methylindenyl)tribenzylzirconium, 0211 (m-cyclopentadienyl)(m-2-chlorofluorenyl)Zirco 0246 (m-4-bromo-2-methylindenyl)trimethoxyzirco nium dichloride, nium, 0212 (m-cyclopentadienyl)(m-2-fluorofluorenyl)Zirco 0247 (m-4-bromo-2-methylindenyl)-tris(dimethy nium dichloride, lamino)Zirconium, 0213 (m-cyclopentadienyl)(m-2,7-dibromofluorenyl) 10248 (m-3-(4-bromophenyl-cyclopentadienyl)zirco Zirconium dichloride, nium trichloride, 0214) (m-cyclopentadienyl)(m-7-bromoindeno1.2-c. (0249 (m-4-bromo-2-methylcyclopentablnaphthyl)zir pyridinyl)Zirconium dichloride, conium trichloride, 0215 (m-cyclopentadienyl)(m-3-bromoindeno1,2-c. (0250 (m-8-bromo-6-methylindeno.5,6-d1.3dioxolyl) pyridinyl)Zirconium dichloride, Zirconium trichloride, 0216 (m-cyclopentadienyl)(m-7-bromoindeno1,2-c. 0251 (m-4-bromo-2,3,6-trimethylindeno.5,6-bithienyl) phosphoranyl)Zirconium dichloride, Zirconium trichloride, 0217 (m-cyclopentadienyl)(m-2-bromoindeno1,2-b 10252) (m-2-bromo-4,6-dimethylindeno.5,6-bithienyl) thienyl)Zirconium dichloride, Zirconium trichloride, 0218 (m-cyclopentadienyl)(m-6-bromoindeno2.1-b (0253 (m-4-bromo-1,2,3,6-tetramethylcyclopentaflin thienyl)Zirconium dichloride, dolyl)Zirconium trichloride, 0219 (m-cyclopentadienyl)(m-6-bromoindeno1.2-c. (0254 (m-4-bromo-1-phenyl-2,3,6-triamethylcyclopenta thienyl)Zirconium dichloride, glindolyl)Zirconium trichloride, 0220 (m-cyclopentadienyl)(m-6-bromoindeno1,2-b 0255 (m-5-bromo-7-methylcyclopentagguinolyl)Zir thienyl)Zirconium dichloride, conium trichloride, 0221 (m-cyclopentadienyl)(m-6-bromo-2,3-dimethyl 0256 (m-2-bromo-5,7-dimethylcyclopentagguinolyl) indeno 1.2-bfuranyl)Zirconium dichloride, Zirconium trichloride, 0222 (m-cyclopentadienyl)(m-2-bromoindeno1,2-b (0257 (m-4,6-dibromo-2-methylindenyl)zirconium 1 benzothienyl)Zirconium dichloride, trichloride, 0223 (m-cyclopentadienyl)(m-8-bromoindeno1,2-b (0258 (m-4,6-dichloro-2-methylindenyl)zirconium 1 benzothienyl)Zirconium dichloride, trichloride, 0224 (m-cyclopentadienyl)(m-8-bromoindeno.2.1-b 0259 (m-4,6-difluoro-2-methylindenyl)Zirconium 1 benzothienyl)Zirconium dichloride, trichloride, US 2010/01 13717 A1 May 6, 2010 27

0260 (m-4-bromo-6-chloro-2-methylindenyl)zirconium (0292 (m-2-bromoindenyl)Zirconium trichloride, trichloride, 0293 (m-2-bromo-4,7-dimethylindenyl)zirconium 0261) (m-4-bromo-6-fluoro-2-methylindenyl)zirconium trichloride, trichloride, 0294 (m-3-bromoindenyl)Zirconium trichloride, 0262 (m-5-bromo-2,4-dimethylindenyl)zirconium (0295) (m-2-chloroindenyl)zirconium trichloride, trichloride, 0296 (m-2-bromofluorenyl)Zirconium trichloride, 0263 (m-6-bromo-2,4-dimethylindenyl)zirconium (0297 (m-2-iodofluorenyl)zirconium trichloride, trichloride, (0298 (m-2-chlorofluorenyl)zirconium trichloride, 0264 (m-7-bromo-2-methyl-4-phenylindenyl)Zirconium 0299 (m-2-fluorofluorenyl)Zirconium trichloride, trichloride, (0300 (m-2,7-dibromofluorenyl)zirconium trichloride, 0265 (m-3-bromo-5-methylcyclopentablthienyl)Zirco 0301 (m-7-bromoindeno. 1.2-cpyridinyl)Zirconium nium trichloride, trichloride, 0266 (m-1,3-dichlorocyclopentacthienyl)Zirconium 0302 (m-3-bromoindeno. 1.2-cpyridinyl)Zirconium trichloride, trichloride, 0267 (m-8-bromo-2-methylcyclopentab1benzothie (0303 (m-7-bromoindeno1.2-clphosphoranyl)zirconium nyl)Zirconium trichloride, trichloride, 0268 (m-8-chloro-2-methylcyclopentabl1)benzothie (0304 (m-2-bromoindeno1,2-bithienyl)zirconium nyl)Zirconium trichloride, trichloride, 0269 (m-8-iodo-2-methylcyclopentabl1)benzothie (0305 (m-6-bromoindeno.2.1-bithienyl)zirconium nyl)Zirconium trichloride, trichloride, (0270 (m-8-fluoro-2-methylcyclopentab1benzothie (0306 (m-6-bromoindeno1.2-cIthienyl)Zirconium nyl)Zirconium trichloride, trichloride, 0271 (m-3-bromo-5-methylcyclopentablfuryl)Zirco 0307 (m-6-bromoindeno1,2-bithienyl)Zirconium nium trichloride, trichloride, 0272 (m-2-bromo-1,5-dimethylcyclopentablpyrrolyl) 0308 (m-6-bromo-2,3-dimethylindeno1.2-blfuranyl) Zirconium trichloride, Zirconium trichloride, (0273 (m-2-bromo-5-methyl-1-phenylcyclopentablpyr (0309 (m-2-bromoindeno1.2-b1benzothienyl)zirco rolyl)Zirconium trichloride, nium trichloride, (0274 (m-2-chloro-5-methyl-1-phenylcyclopentablpyr 0310 (m-8-bromoindeno1.2-b1benzothienyl)zirco rolyl)Zirconium trichloride, nium trichloride, (0275 (m-2-iodo-5-methyl-1-phenylcyclopentablpyrro 0311 (m-8-bromoindeno.2.1-b1benzothienyl)zirco lyl)Zirconium trichloride, nium trichloride, (0276 (m-2-fluoro-5-methyl-1-phenylcyclopentablpyr 0312 (m-3-bromo-6H-indeno.2.1-bl. 1)benzothienyl) rolyl)Zirconium trichloride, Zirconium trichloride, (0277 (m-2-bromo-1,5-dimethylcyclopentablphospho 0313 (m-2-bromo-5-methylindeno1,2-bindolyl)Zirco lyl)Zirconium trichloride, nium trichloride, 0278 (m-5-bromo-2,4-dimethylcyclopentablindolyl) 0314 (m-8-bromo-5-methylindeno1,2-bindolyl)Zirco Zirconium trichloride, nium trichloride, 0279 (m-4-bromocyclopentablpyridyl)zirconium 0315 (m-8-bromo-5-methylindeno.2.1-bindolyl)Zirco trichloride, nium trichloride, (0280 (m-4-bromocyclopentablphosphoranyl)zirco 0316 (m-3-bromo-5-methylindeno2, 1-bindolyl)zirco nium trichloride, nium trichloride, (0281) (m-2,6-dibromo-1-dimethylamino-1-boratoben 0317 (m-2-5-bromonaphth-1-ylindenyl)zirconium tri Zene)Zirconium trichloride, bromide, 0282 (m-4-bromo-3-dimethylamini-1,3-thiaborindenyl) 0318 (m-2-7-fluorobenzothien-2-ylindenyl)zirconium Zirconium trichloride, tribromide, (0283 (m-4-bromo-3a,7a-azaborindenyl)Zirconium 0319 (m-2-[2-chlorobenzothien-4-ylindenyl)Zirconium trichloride, tribromide, (0284 (m-7-bromo-2-dimethylamino-1,2-benzothiabo 0320 rac-dimethylsilanediyl-bis(m-4-bromo-2-methyl ralide)Zirconium trichloride, inden-1-yl)Zirconium dichloride, (0285) (m-3-bromo-2-dimethylamino-1,2-thiaborollide) 0321) rac-dimethylsilanediyl-bis(m-4-bromoinden-1-yl) Zirconium trichloride, Zirconium dichloride, (0286 (m-2-(4-bromophenyl)-indenyl)zirconium trichlo 10322 rac-dimethylsilanediyl-bis(m-4-bromo-2-isopro ride, pylinden-1-yl)Zirconium dichloride, 0287) (m-2-4-chlorophenyl-indenyl)Zirconium trichlo 0323 rac-dimethylsilanediyl-bis(m-4-bromo-2-phenyl ride, inden-1-yl)Zirconium dichloride, 0288 (m-2-4-fluorophenyl-indenyl)zirconium trichlo 0324 rac-dimethylsilanediyl-bis(m-4-bromo-2-5-me ride, thyl-2-thienylinden-1-yl)Zirconium dichloride, (0289 (m-2-4-iodophenyl-indenyl)zirconium trichlo 0325 rac-dimethylsilanediyl-bis(m-4-bromo-2-4-py ride, ridinylinden-1-yl)Zirconium dichloride, 0290 (m-2-5-bromothien-2-yl)-indenyl)zirconium 10326) rac-dimethylsilanediyl-bis(m-4-fluoro-2-methyl trichloride, inden-1-yl)Zirconium dichloride, 0291 (m-2-4-bromopyridin-2-yl)-indenyl)Zirconium 0327 rac-dimethylsilanediyl-bis(m-4-chloro-2-methyl trichloride, inden-1-yl)Zirconium dichloride,

US 2010/01 13717 A1 May 6, 2010 41

1116) dimethylsilanediyl(m-6-bromo-2,3-dimethylin 1141 (m-2-methyl-4-(m-tolyl)indenyl)(m-pentamethyl deno1,2-bfuran-4-yl)(tert-butylamido)Zirconium dichlo cyclopentadienyl)Zirconium dichloride, ride, (1142 (m-2-methyl-4-(o-tolyl)indenyl)(m-pentamethyl 1117 dimethylsilanediyl(m-2-bromoindeno1.2-b1 cyclopentadienyl)Zirconium dichloride, benzothien-10-yl)(tert-butylamido)Zirconium dichloride, 1143 (m-2-methyl-4-(4-t-butylphenyl)indenyl)(m-pen 1118 dimethylsilanediyl(m-8-bromoindeno. 1.2-bl1 tamethylcyclopentadienyl)Zirconium dichloride, benzothien-10-yl)(tert-butylamido)Zirconium dichloride, (1144 (m-2-methyl-4-(4-fluorophenyl)indenyl)(m-pen 1119 dimethylsilanediyl(m-8-bromoindeno.2.1-bl.1 tamethylcyclopentadienyl)Zirconium dichloride, benzothien-6-yl)(tert-butylamido)Zirconium dichloride, 1145 (m-2-methyl-4-(3-trifluoromethylphenyl)indenyl) 1120 dimethylsilanediyl(m-3-bromoindeno.2.1-bl.1 (m-pentamethylcyclopentadienyl)Zirconium dichloride, benzothien-6-yl)(tert-butylamido)Zirconium dichloride, 1146 (m-2-methyl-4-(2-methoxyphenyl)indenyl)(m- 1121 dimethylsilanediyl(m-2-bromo-5-methylindeno1, pentamethylcyclopentadienyl)Zirconium dichloride, 2-bindol-10-yl)(tert-butylamido)Zirconium dichloride, 1147 (m-2-methyl-4-(4-biphenyl)bromoindenyl)(m- 1122 dimethylsilanediyl(m-8-bromo-5-methylindeno1, pentamethylcyclopentadienyl)Zirconium dichloride, 2-bindol-10-yl)(tert-butylamido)Zirconium dichloride, 1148 (m-2-methyl-4-(1-naphthyl)indenyl)(m-pentam 1123 dimethylsilanediyl(m-8-bromo-5-methylindeno2, ethylcyclopentadienyl)Zirconium dichloride, 1-bindol-6-yl)(tert-butylamido)Zirconium dichloride, (1149 (m-2-methyl-4-(2-thienyl)indenyl)(m-pentameth ylcyclopentadienyl)Zirconium dichloride, 1124 dimethylsilanediyl(m-3-bromo-5-methylindeno2, 1150 (m-2-methyl-4-(2-benzothienyl)indenyl)(m-pen 1-bindol-6-yl)(tert-butylamido)Zirconium dichloride, tamethylcyclopentadienyl)Zirconium dichloride, 1125 dimethylsilandiyl(m-2-5-bromonaphth-1-ylin 1151) (m-2-methyl-4-(2-furyl)indenyl)(m-pentamethyl den-1-yl)(tert-butylamido)Zirconium dichloride, cyclopentadienyl)Zirconium dichloride, 1126 dimethylsilandiyl(m-2-7-fluorobenzothien-2-yl) 1152 (m-2-methyl-4-(2-benzofuryl)indenyl)(m-pen inden-1-yl)(tert-butylamido)Zirconium dichloride, tamethylcyclopentadienyl)Zirconium dichloride, 1127 dimethylsilandiyl(m-2-[2-chlorobenzothien-4-yl) 1153 (m-2-methyl-4-styrylindenyl)(m-pentamethylcy inden-1-yl)(tert-butylamido)Zirconium dichloride, clopentadienyl)Zirconium dichloride (cis and trans), 1128 (5-bromonaphth-1-yl)methylideno-(m-2,3,4,5-tet 1154 (m-2-methyl-4-(4-fluorostyryl)indenyl)(m-pen ramethycyclopentadien-1-yl)(tert-butylamido)Zirconium tamethylcyclopentadienyl)Zirconium dichloride (trans), dichloride, 1155 (m-2-methyl-4-(1,2-butoxyvinyl)indenyl)(m-pen 1129 (7-fluorobenzothien-2-yl)methylideno-(m-2,3,4, tamethylcyclopentadienyl)Zirconium dichloride, 5-tetramethycyclopentadien-1-yl)(tert-butylamido)Zirco (1156 (m-2,4-dimethylindenyl)(m-pentamethylcyclo nium dichloride, pentadienyl)hafnium dichloride, 1130 (2-chlorobenzothien-4-yl)methylideno-(m-2.3.4. (1157 (m-2-methyl-4-phenylindenyl)(m-pentamethylcy 5-tetramethycyclopentadien-1-yl)(tert-butylamido)Zirco clopentadienyl)hafnium dichloride, nium dichloride, 1158 (m-2-methyl-4-(p-tolyl)indenyl)(m-pentamethyl 1131 dimethylsilandiyl(m-2,3,4,5-tetramethycyclopen cyclopentadienyl)hafnium dichloride, tadien-1-yl)(5-bromonaphth-1-yl)Zirconium dichloride, 1159 (m-2-methyl-4-(m-tolyl)indenyl)(m-pentamethyl 1132 dimethylsilandiyl(m-2,3,4,5-tetramethycyclopen cyclopentadienyl)hafnium dichloride, tadien-1-yl)(7-fluorobenzothien-2-y)Zirconium dichlo 1160 (m-2-methyl-4-(o-tolyl)indenyl)(m-pentamethyl ride, cyclopentadienyl)hafnium dichloride, 1133 dimethylsilandiyl(m-2,3,4,5-tetramethycyclopen 1161) (m-2-methyl-4-(4-t-butylphenyl)indenyl)(m-pen tadien-1-yl)(2-chlorobenzothien-4-yl)Zirconium dichlo tamethylcyclopentadienyl)hafnium dichloride, ride, and 1162 (m-2-methyl-4-(4-fluorophenyl)indenyl)(m-pen 1134 the hafnium and titanium analogs of the examples tamethylcyclopentadienyl)hafnium dichloride, above. 1163 (m-2-methyl-4-(3-trifluoromethylphenyl)indenyl) 1135 Methods of synthesizing the halogen substituted (m-pentamethylcyclopentadienyl)hafnium dichloride, metallocene compounds listed above are disclosed in our 1164 (m-2-methyl-4-(2-methoxyphenyl)indenyl)(m- copending U.S. patent application Ser. Nos. 1 1/302.798, pentamethylcyclopentadienyl)hafnium dichloride, 11/300,240, 11/300,032 (now U.S. Pat. No. 7,557,171), 1165 (m-2-methyl-4-(4-biphenyl)bromoindenyl)(m- 11/300.0029 (now U.S. Pat. No. 7,538,168), 11/300,054 pentamethylcyclopentadienyl)hafnium dichloride, (now U.S. Pat. No. 7,446.216), 11/302,381 (now U.S. Pat. 1166 (m-2-methyl-4-(1-naphthyl)indenyl)(m-pentam No. 7.550,544) all filed concurrently herewith and all incor ethylcyclopentadienyl)hafnium dichloride, porated herein by reference. 1167 (m-2-methyl-4-(2-thienyl)indenyl)(m-pentameth 1136. A set of exemplary catalyst precursor prepared by ylcyclopentadienyl)hafnium dichloride, coupling or cross-coupling reactions is set out below. These 1168 (m-2-methyl-4-(2-benzothienyl)indenyl)(m-pen are by way of example only and are not intended to list every tamethylcyclopentadienyl)hafnium dichloride, catalyst precursor that is within the scope of the invention. 1169 (m-2-methyl-4-(2-furyl)indenyl)(m-pentamethyl 1137 Preferred compounds include: cyclopentadienyl)hafnium dichloride, 1138 (m-2,4-dimethylindenyl)(m-pentamethylcyclo 1170 (m-2-methyl-4-(2-benzofuryl)indenyl)(m-pen pentadienyl)Zirconium dichloride, tamethylcyclopentadienyl)hafnium dichloride, 1139 (m-2-methyl-4-phenylindenyl)(m-pentamethylcy 1171) (m-2-methyl-4-styrylindenyl)(m-pentamethylcy clopentadienyl)Zirconium dichloride, clopentadienyl)hafnium dichloride (cis and trans), 1140 (m-2-methyl-4-(p-tolyl)indenyl)(m-pentamethyl 1172 (m-2-methyl-4-(4-fluorostyryl)indenyl)(m-pen cyclopentadienyl)Zirconium dichloride, tamethylcyclopentadienyl)hafnium dichloride (trans), and

US 2010/01 13717 A1 May 6, 2010 46

1410) dimethylsilyl(m-4,5-dimethylcyclopentablthien enylboron, tris-perfluorophenylboron, tris-perfluorophenyl 6-yl)(m-4-(4-dimethylaminophenyl)-2,6-diisopropylphe aluminum and the like; Ionic activators include dimethyla nylamido)titanium dichloride, nilinium tetrakis perfluorophenyl borate, triphenyl car 1411 dimethylsilyl(m-4,5-dimethylcyclopentablthien bonium tetrakis perfluorophenyl borate, dimethylanilinium 6-yl)(m-4-(2-benzofuryl)-2,6-diisopropylphenylamido) tetrakis perfluorophenyl aluminate, and the like. titanium dichloride, 1429. A co-activator is a compound capable of alkylating 1412 dimethylsilyl(m-4,5-dimethylcyclopentablthien the transition metal complex, Such that when used in combi 6-yl)(m-2,4,6-trimethylphenylamido)titanium dichloride, nation with an activator, an active catalyst is formed. Co 1413 dimethylsilyl(m-4,5-dimethylcyclopentablthien activators include alumoxanes Such as methyl alumoxane, 6-yl)(m-4-(p-tolyl)-2,6-dimethylphenylamido)Zirconium modified alumoxanes such as modified methyl alumoxane, dichloride, and aluminum alkyls such as trimethylaluminum, tri-isobutyl 1414) dimethylsilyl(m-4,5-dimethylcyclopentablthien aluminum, triethyl aluminum, and tri-isopropyl aluminum. 6-yl)(m-4-methyl-2,6-diisopropylphenylamido)Zirco Co-activators are typically only used in combination with nium dichloride, Lewis acid activators and ionic activators when the precata 1415) dimethylsilyl(m-4,5-dimethylcyclopentablthien lyst is not a dihydrocarbyl or dihydride complex. 6-yl)(m-4-(p-tolyl)-2,6-diisopropylphenylamido)Zirco 1430. The alumoxane component useful as an activator nium dichloride, typically is an oligomeric aluminum compound represented 1416) dimethylsilyl(m-4,5-dimethylcyclopentablthien by the general formula (R—Al-O), which is a cyclic com 6-yl)(m-4-(3-trifluoromethylphenyl)-2,6-diisopropylphe pound, or R (R Al-O),AlR, which is a linear com nylamido)Zirconium dichloride, pound. In the general alumoxane formula, R is indepen 1417 dimethylsilyl(m-4,5-dimethylcyclopentablthien dently a C-C alkyl radical, for example, methyl, ethyl, 6-yl)(m-4-(4-dimethylaminophenyl)-2,6-diisopropylphe propyl, butyl, pentyl, isomers thereof, and the like, and “n” is nylamido)Zirconium dichloride, an integer from 1-50. Most preferably, R is methyl and “n” is 1418 dimethylsilyl(m-4,5-dimethylcyclopentablthien at least 4. Methyl alumoxane and modified methyl alumox 6-yl)(m-4-(2-benzofuryl)-2,6-diisopropylphenylamido) anes are most preferred. For further descriptions see, EPO 279 Zirconium dichloride, 586, EP 0594218, EP 0561476, WO94/10180 and U.S. Pat. 1419 dimethylsilyl(m-4,5-dimethylcyclopentablthien Nos. 4,665,208, 4,874,734, 4,908,463, 4,924,018, 4,952,540, 6-yl)(m-2,4,6-trimethylphenylamido)Zirconium dichlo 4,968,827, 5,041584, 5,091,352, 5,103,031, 5,157,137, ride, 5,204,419, 5,206,199, 5,235,081, 5,248,801, 5,329,032, 1420 dimethylsilyl(m-4,5-dimethylcyclopentablthien 5,391,793, and 5,416,229. 6-yl)(m-4-(p-tolyl)-2,6-dimethylphenylamido)hafnium 1431. When analumoxane or modified alumoxane is used, dichloride, the catalyst-precursor-to-activator molar ratio is from about 1421 dimethylsilyl(m-4,5-dimethylcyclopentablthien 1:3000 to 10:1; alternatively, 1:2000 to 10:1; alternatively 6-yl)(m-4-methyl-2,6-diisopropylphenylamido)hafnium 1:1000 to 10:1; alternatively, 1:500 to 1:1; alternatively 1:300 dichloride, to 1:1; alternatively 1:200 to 1:1; alternatively 1:100 to 1:1; 1422 dimethylsilyl(m-4,5-dimethylcyclopentablthien alternatively 1:50 to 1:1; alternatively 1:10 to 1:1. When the 6-yl)(m-4-(p-tolyl)-2,6-diisopropylphenylamido) activator is an alumoxane (modified or unmodified), some hafnium dichloride, embodiments select the maximum amount of activator at a 1423 dimethylsilyl(m-4,5-dimethylcyclopentablthien 5000-fold molar excess over the catalyst precursor (per metal 6-yl)(m-4-(3-trifluoromethylphenyl)-2,6-diisopropylphe catalytic site). The preferred minimum activator-to-catalyst nylamido)hafnium dichloride, precursor ratio is 1:1 molar ratio. 1424 dimethylsilyl(m-4,5-dimethylcyclopentablthien 1432 Ionic activators (at times used in combination with a 6-yl)(m-4-(4-dimethylaminophenyl)-2,6-diisopropylphe co-activator) may be used in the practice of this invention. nylamido)hafnium dichloride, Preferably, discrete ionic activators such as MePhNHIB 1425) dimethylsilyl(m-4,5-dimethylcyclopentablthien (CFs). PhCIB(CFs). MePhNHIB((CH-3,5- 6-yl)(m-4-(2-benzofuryl)-2,6-diisopropylphenylamido) (CF))), PhCIB((CH-3,5-(CF))), INHIB(CHs) hafnium dichloride, and or Lewis acidic activators such as B(CFs) or B(C6Hs). 1426) dimethylsilyl(m-4,5-dimethylcyclopentablthien can be used. Preferred co-activators, when used, are alumox 6-yl)(m-2,4,6-trimethylphenylamido)hafnium dichloride. anes such as methyl alumoxane, modified alumoxanes Such 1427. In a preferred embodiment any of the catalyst pre as modified methyl alumoxane, and aluminum alkyls such as cursors listed above (prepared by coupling or cross-coupling tri-isobutyl aluminum, and trimethyl aluminum. reactions) is combined with an activator to form a catalyst 1433. It is within the scope of this invention to use an system. Preferably Such catalysts systems are used to poly ionizing or stoichiometric activator, neutral or ionic, such as merize olefins, such as ethylene and or propylene. tri (n-butyl)ammonium tetrakis(pentafluorophenyl)borate, a trisperfluorophenyl boron metalloid precursor or a trisper Activators and Catalyst Activation fluoronaphthyl boron metalloid precursor, polyhalogenated 1428. The substituted metallocene compounds produced heteroborane anions (WO 98/43983), boric acid (U.S. Pat. by the process described above are useful as catalyst precur No. 5,942.459) or combination thereof. sors and, when activated with activators, such as methyl alu 1434 Examples of neutral stoichiometric activators moxane or a non-coordinating anion, form active catalysts for include tri-substituted boron, tellurium, aluminum, gallium the polymerization or oligomerization of olefins. Activators and indium or mixtures thereof. The three substituent groups that may be used include alumoxanes such as methyl alumox are each independently selected from alkyls, alkenyls, halo ane, modified methyl alumoxane, ethyl alumoxane, iso-butyl gen, Substituted alkyls, aryls, arylhalides, alkoxy and halides. alumoxane and the like; Lewis acid activators include triph Preferably, the three groups are independently selected from US 2010/01 13717 A1 May 6, 2010 47 halogen, mono or multicyclic (including halosubstituted) 1440. The activating cation (L**-H) may be a Bronsted aryls, alkyls, and alkenyl compounds and mixtures thereof, acid, capable of donating a proton to the alkylated transition preferred are alkenyl groups having 1 to 20 carbon atoms, metal catalytic precursor resulting in a transition metal cation, alkyl groups having 1 to 20 carbon atoms, alkoxy groups including ammoniums, oxoniums, phosphoniums, silyliums, having 1 to 20 carbon atoms and aryl groups having 3 to 20 and mixtures thereof, preferably ammoniums of methy carbon atoms (including substituted aryls). More preferably, lamine, aniline, dimethylamine, diethylamine, N-methyla the three groups are alkyls having 1 to 4 carbon groups, niline, diphenylamine, trimethylamine, triethylamine, N.N- phenyl, naphthyl or mixtures thereof. Even more preferably, dimethylaniline, methyldiphenylamine, pyridine, p-bromo the three groups are halogenated, preferably fluorinated, aryl N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phos groups. Most preferably, the neutral stoichiometric activator phoniums from triethylphosphine, triphenylphosphine, and is trisperfluorophenylboron or trisperfluoronaphthylboron. diphenylphosphine, oxomiuns from ethers such as dimethyl 1435. Ionic stoichiometric activator compounds may con ether, diethyl ether, tetrahydrofuran and dioxane, sulfoniums tain an active proton, or Some other cation associated with, but from thioethers, such as diethyl thioethers and tetrahy not coordinated to, or only loosely coordinated to, the remain drothiophene, and mixtures thereof. The activating cation ing ion of the ionizing compound. Such compounds and the (L**-H) may also be a moiety such as silver, tropylium, like are described in European publications EP-A-0570982, carbeniums, ferroceniums and mixtures, preferably carboni EP-A-0520 732, EP-A-0495 375, EP B1-0 500 944, EP ums and ferroceniums; most preferably triphenyl carbonium. A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153, 1441. The anion component A' include those having the 157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 formula M'Q,' whereinkis an integer from 1 to 3; n is an and 5,502,124 and U.S. patent application Ser. No. 08/285, integer from 2-6; n-k=d; M is an element selected from 380, filed Aug. 3, 1994, all of which are herein fully incorpo Group 13 of the Periodic Table of the Elements, preferably rated by reference. boron or aluminum, and Q is independently a hydride, 1436 Ionic catalysts can be prepared by reacting a transi bridged or unbridged dialkylamido, halide, alkoxide, arylox tion metal compound with an activator, Such as B(CF). ide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substi which upon reaction with the hydrolyzable ligand (X) of the tuted halocarbyl, and halosubstituted-hydrocarbyl radicals, transition metal compound forms an anion, such as (IB(CFs) said Q having up to 20 carbon atoms with the proviso that in (X)), which stabilizes the cationic transition metal species not more than one occurrence is Qahalide. Preferably, each generated by the reaction. The catalysts can be, and prefer Q is a fluorinated hydrocarbyl group having 1 to 20 carbon ably are, prepared with activator components which are ionic atoms, more preferably each Q is a fluorinated aryl group, and compounds or compositions. However preparation of activa most preferably each Q is a pentafluorylaryl group. Examples tors utilizing neutral compounds is also contemplated by this of suitable A" also include diboron compounds as disclosed invention. in U.S. Pat. No. 5,447.895, which is fully incorporated herein 1437 Compounds useful as an activator component in the by reference. preparation of the ionic catalyst Systems used in the process of 1442 Illustrative, but not limiting examples of boroncom this invention comprise a cation, which is preferably a Bron pounds which may be used as an activating cocatalyst in sted acid capable of donating a proton, and a compatible combination with a co-activator in the preparation of the non-coordinating anion which anion is relatively large improved catalysts of this invention are tri-Substituted ammo (bulky), capable of stabilizing the active catalyst species nium salts such as: which is formed when the two compounds are combined and 1443 trimethylammonium tetraphenylborate, said anion will be sufficiently labile to be displaced by ole 1444 triethylammonium tetraphenylborate, finic diolefinic and acetylenically unsaturated Substrates or 1445 tripropylammonium tetraphenylborate, other neutral Lewis bases such as ethers, nitriles and the like. 1446 tri(n-butyl)ammonium tetraphenylborate, Two classes of compatible non-coordinating anions have 1447 tri(tert-butyl)ammonium tetraphenylborate, been disclosed in EPA 277,003 and EPA 277,004 published 1448 N.N-dimethylanilinium tetraphenylborate, 1988: 1) anionic coordination complexes comprising a plu rality of lipophilic radicals covalently coordinated to and 1449 N,N-diethylanilinium tetraphenylborate, shielding a central charge-bearing metal or metalloid core, 1450 N.N-dimethyl-(2,4,6-trimethylanilinium)tetraphe and 2) anions comprising a plurality of boronatoms such as nylborate, carboranes, metallacarboranes and boranes. 1451 trimethylammonium tetrakis(pentafluorophenyl) 1438. In a preferred embodiment, the stoichiometric acti borate, vators include a cation and an anion component, and may be 1452 triethylammonium tetrakis(pentafluorophenyl)bo represented by the following formula: rate, 1453 tripropylammonium tetrakis(pentafluorophenyl) borate, wherein L** is an neutral Lewis base; 1454 tri(n-butyl)ammonium tetrakis(pentafluorophenyl) His hydrogen; borate, (L**-H)" is a Bronsted acid 1455 tri(sec-butyl)ammonium tetrakis(pentafluorophe A is a non-coordinating anion having the charge d nyl)borate, d is an integer from 1 to 3. 1456 N.N-dimethylanilinium tetrakis(pentafluorophe 1439. The cation component, (L*-H) may include nyl)borate, Bronsted acids such as protons or protonated Lewis bases or 1457 N,N-diethylanilinium tetrakis(pentafluorophenyl) reducible Lewis acids capable of protonating or abstracting a borate, moiety, such as an alkyl or aryl, from the precatalyst after 1458 N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis alkylation. (pentafluorophenyl)borate, US 2010/01 13717 A1 May 6, 2010 48

1459 trimethylammonium tetrakis-(2,3,4,6-tetrafluo and dialkyl ammonium salts such as: rophenyl)borate, 1491 di-(iso-propyl)ammonium tetrakis(pentafluorophe 1460 triethylammonium tetrakis-(2,3,4,6-tetrafluorophe nyl)borate, and nyl)borate, 1492 dicyclohexylammonium tetrakis(pentafluorophe 1461 tripropylammonium tetrakis-(2,3,4,6-tetrafluo nyl)borate; rophenyl)borate, and other salts such as: 1462 tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluo 1493 tri(o-tolyl)phosphonium tetrakis(pentafluorophe rophenyl)borate, nyl)borate, 1463 dimethyl(tert-butyl)ammonium tetrakis-(2,3,4,6- 1494 tri(2,6-dimethylphenyl)phosphonium tetrakis(pen tetrafluorophenyl)borate, tafluorophenyl)borate, 1464 N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluo 1495 tropillium tetraphenylborate, rophenyl)borate, 1496 triphenylcarbenium tetraphenylborate, 1465 N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluo 1497 triphenylphosphonium tetraphenylborate, rophenyl)borate, 1498 triethylsilylium tetraphenylborate, 1466 N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis 1499 benzene(diazonium)tetraphenylborate, (2,3,4,6-tetrafluorophenyl)borate, 1500 tropillium tetrakis(pentafluorophenyl)borate, 1467 trimethylammonium tetrakis(perfluoronaphthyl) 1501 triphenylcarbenium tetrakis(pentafluorophenyl)bo borate, rate, 1468 triethylammonium tetrakis(perfluoronaphthyl)bo 1502 triphenylphosphonium tetrakis(pentafluorophenyl) rate, borate, 1469 tripropylammonium tetrakis(perfluoronaphthyl) 1503 triethylsilylium tetrakis(pentafluorophenyl)borate, borate, 1504 benzene(diazonium)tetrakis(pentafluorophenyl) 1470 tri(n-butyl)ammonium tetrakis(perfluoronaphthyl) borate, borate, 1505 tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)bo 1471 tri(tert-butyl)ammonium tetrakis(perfluoronaph rate, thyl)borate, 1506 triphenylcarbenium tetrakis-(2,3,4,6-tetrafluo 1472 N,N-dimethylanilinium tetrakis(perfluoronaph rophenyl)borate, thyl)borate, 1507 triphenylphosphonium tetrakis-(2,3,4,6-tetrafluo 1473 N,N-diethylanilinium tetrakis(perfluoronaphthyl) rophenyl)borate, borate, 1508 triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl) 1474 N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis borate, (perfluoronaphthyl)borate, 1509 benzene(diazonium)tetrakis-(2,3,4,6-tetrafluo 1475 trimethylammonium tetrakis(perfluorobiphenyl) rophenyl)borate, borate, 1510 tropillium tetrakis(perfluoronaphthyl)borate, 1476 triethylammonium tetrakis(perfluorobiphenyl)bo 1511 triphenylcarbenium tetrakis(perfluoronaphthyl)bo rate, rate, 1477 tripropylammonium tetrakis(perfluorobiphenyl) 1512 triphenylphosphonium tetrakis(perfluoronaphthyl) borate, borate, 1478 tri(n-butyl)ammonium tetrakis(perfluorobiphenyl) 1513 triethylsilylium tetrakis(perfluoronaphthyl)borate, borate, 1514 benzene(diazonium)tetrakis(perfluoronaphthyl)bo 1479 tri(tert-butyl)ammonium tetrakis(perfluorobiphe rate, nyl)borate, 1515 tropillium tetrakis(perfluorobiphenyl)borate, 1480 N.N-dimethylanilinium tetrakis(perfluorobiphe 1516 triphenylcarbenium tetrakis(perfluorobiphenyl)bo nyl)borate, rate, 1481 N,N-diethylanilinium tetrakis(perfluorobiphenyl) 1517 triphenylphosphonium tetrakis(perfluorobiphenyl) borate, borate, 1482 N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis 1518 triethylsilylium tetrakis(perfluorobiphenyl)borate, (perfluorobiphenyl)borate, 1519 benzene(diazonium)tetrakis(perfluorobiphenyl)bo 1483 trimethylammonium tetrakis(3,5-bis(trifluorom rate, ethyl)phenyl)borate, 1520 tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl) 1484 triethylammonium tetrakis(3,5-bis(trifluorom borate, ethyl)phenyl)borate, 1521 triphenylcarbenium tetrakis(3,5-bis(trifluorom 1485 tripropylammonium tetrakis(3,5-bis(trifluorom ethyl)phenyl)borate, ethyl)phenyl)borate, 1522 triphenylphosphonium tetrakis(3,5-bis(trifluorom 1486 tri(n-butyl)ammonium tetrakis(3,5-bis(trifluorom ethyl)phenyl)borate, ethyl)phenyl)borate, 1523 triethylsilylium tetrakis(3,5-bis(trifluoromethyl) 1487 tri(tert-butyl)ammonium tetrakis(3,5-bis(trifluo phenyl)borate, and romethyl)phenyl)borate, 1524 benzene(diazonium)tetrakis(3,5-bis(trifluorom 1488 N,N-dimethylanilinium tetrakis(3,5-bis(trifluo ethyl)phenyl)borate. romethyl)phenyl)borate, 1525 Most preferably, the ionic stoichiometric activator 1489 N,N-diethylanilinium tetrakis(3,5-bis(trifluorom (L*-H)." (A') is N,N-dimethylanilinium tetrakis(perfluo ethyl)phenyl)borate, rophenyl)borate, 1490 N.N-dimethyl-(2,4,6-trimethylanilinium)tetrakis 1526 N,N-dimethylanilinium tetrakis(perfluoronaph (3,5-bis(trifluoromethyl)phenyl)borate, thyl)borate, US 2010/01 13717 A1 May 6, 2010 49

1527 N,N-dimethylanilinium tetrakis(perfluorobiphe catalyst precursor-to-activator molar ratio may be any ratio. nyl)borate, Combinations of the described activator compounds may also 1528 N,N-dimethylanilinium tetrakis(3,5-bis(trifluo be used for activation. romethyl)phenyl)borate, 1539 When an ionic or neutral stoichiometric activator is 1529 triphenylcarbenium tetrakis(perfluoronaphthyl)bo used, the catalyst precursor-to-activator molar ratio is from rate, 1:10 to 1:1:1:10 to 10:1; 1:10 to 2:1:1:10 to 3:1:1:10 to 5:1; 1530 triphenylcarbenium tetrakis(perfluorobiphenyl)bo 1:2 to 1.2:1:1:2 to 10:1:1:2 to 2:1:1:2 to 3:1:1:2 to 5:1:1:3 to 1.2:1:1:3 to 10:1; 1:3 to 2:1:1:3 to 3:1; 1:3 to 5:1; 1:5 to rate, 1:1:1:5 to 10:1; 1:5 to 2:1:1:5 to 3:1:1:5 to 5:1:1:1 to 1:1.2. 1531 triphenylcarbenium tetrakis(3,5-bis(trifluorom The catalyst-precursor to-co-activator molar ratio is from ethyl)phenyl)borate, or 1:100 to 100:1:1:75 to 75:1:1:50 to 50:1:1:25 to 25:1:1:15 1532 triphenylcarbenium tetra(perfluorophenyl)borate. to 15:1:1:10 to 10:1; 1:5 to 5:1, 1:2 to 2:1:1:100 to 1:1:1:75 1533. In a preferred embodiment, the activator is trispen to 1:1:1:50 to 1:1:1:25 to 1:1:1:15 to 1:1:1:10 to 1:1:1:5 to tafluorophenylborane. 1:1:1:2 to 1:1:1:10 to 2:1. 1534 Invention catalyst precursors can also be activated 1540 Preferred activators and activator/co-activator com with cocatalysts or activators that comprise non-coordinating binations include methylalumoxane, modified methylalu anions containing metalloid-free cyclopentadienide ions. moxane, mixtures of methylalumoxane with dimethyla These are described in U.S. Patent Publication 2002/0058765 nilinium tetrakis(pentafluorophenyl)borate or tris A1, published on 16 May 2002, and for the instant invention, (pentafluorophenyl)boron, and mixtures of trimethyl require the addition of a co-activator to the catalyst precursor. aluminum with dimethylanilinium tetrakis(pentafluorophe 1535. The term “non-coordinating anion (NCA) means nyl)borate or tris(pentafluorophenyl)boron. an anion that does not coordinate to the catalyst metal cation 1541. In some embodiments, Scavenging compounds are or that does coordinate to the metal cation, but only weakly. used with Stoichiometric activators. Typical aluminum or An NCA coordinates weakly enough that a neutral Lewis boron alkyl components useful as scavengers are represented base, such as an olefinically or acetylenically unsaturated by the general formula RJ"Z", where J" is aluminum or monomer can displace it from the catalyst center. "Compat boron, R is as previously defined above, and each Z" is ible' non-coordinating anions are those which are not independently R' or a different univalent anionic ligand such degraded to neutrality when the initially formed complex as halogen (C1, Br, I), alkoxide (OR) and the like. Most decomposes. Further, the anion will not transfer an anionic preferred aluminum alkyls include triethylaluminum, diethy Substituent or fragment to the cation so as to cause it to form laluminum chloride, tri-iso-butylaluminum, tri-n-octylalu a neutral transition metal compound and a neutral by-product minum, tri-n-hexylaluminum, trimethylaluminum and the from the anion. Non-coordinating anions useful in accor like. Preferred boron alkyls include triethylboron. Scaveng dance with this invention are those that are compatible, sta ing compounds may also be alumoxanes and modified alu bilize the transition metal complex cation in the sense of moxanes including methylalumoxane and modified methyla balancing its ionic charge at +1, yet retain Sufficient lability to lumoxane. permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization. These types of Mixed Catalysts cocatalysts sometimes use Scavengers such as but not limited 1542. The metallocene compounds of the invention can to tri-iso-butyl aluminum, tri-n-octyl aluminum, tri-n-hexyl also be used in mixed catalyst systems where, for example, aluminum, triethylaluminum or trimethylaluminum. the invention catalyst is used in conjunction with a 'second 1536. The present process also can employ cocatalyst catalyst” in the same reactor or in a series of reactors and compounds or activator compounds that are initially neutral where the invention catalyst produces oligomers, macromers, Lewis acids but form a cationic metal complex and a nonco or polymers with olefinic end-groups, and the “second cata ordinating anion, or a Zwitterionic complex upon reaction lyst” incorporates these oligomers, macromers, or polymers with alkylated transition metal compounds. For example, tris into a polymer backbone as a copolymer with other mono (pentafluorophenyl) boron or aluminum acts to abstract a mers, such as ethylene, propylene, butene, and other C2 to hydrocarbyl ligand to yield a cationic transition metal com C20 olefins. Alternatively, the invention catalyst can be used plex and stabilizing noncoordinating anion, see EP-A-0427 in conjunction with a second catalyst in the same reactor or in 697 and EP-A-0 520 732 for illustrations of analogous a series of reactors where the second catalyst produces oligo Group-4 metallocene compounds. Also, see the methods and mers, macromers, or polymers with olefinic end-groups, and compounds of EP-A-0495.375. For formation of Zwitterionic the invention catalyst incorporates these oligomers, mac complexes using analogous Group 4 compounds, see U.S. romers, or polymers into a polymer backbone as a copolymer Pat. Nos. 5,624,878; 5,486,632; and 5,527,929. with other monomers, such as ethylene, propylene, butene, 1537 Additional neutral Lewis-acids are known in the art and other C2 to C20 olefins. The “second catalyst” can be of and are suitable for abstracting formal anionic ligands. See in the same family as the invention catalyst, or can be from a particular the review article by E.Y.-X. Chen and T.J. Marks, completely different catalyst family. Likewise, the invention “Cocatalysts for Metal-Catalyzed Olefin Polymerization: catalyst can be used in conjunction with a 'second catalyst” in Activators, Activation Processes, and Structure-Activity the same reactor or in a series of reactors where the invention Relationships', Chem. Rev., 100, 1391-1434 (2000). catalyst and the 'second catalyst” produces mixtures or 1538. When the cations of noncoordinating anion precur blends of polymers. sors are Bronsted acids Such as protons or protonated Lewis 1543) Suitable additional olefin polymerization catalysts bases (excluding water), or reducible Lewis acids such as for use as the 'second catalyst” in a mixed catalyst system ferrocenium or silvercations, or alkali or alkaline earth metal include any of the compositions well known in the art to cations such as those of sodium, magnesium or lithium, the catalyze the olefin to polyolefin reaction. For example, the US 2010/01 13717 A1 May 6, 2010 50

'second catalyst” can include any Group 4-6 metallocene material for 1 minute to 10 hours. The total solution volume compound, Such as the bridged and unbridged compounds may be greater than the pore Volume of the Support, but some containing one or two cyclopentadienyl-containing ligands. embodiments limit the total solution volume below that Typical catalysts and their precursors are well known in the needed to form agel or slurry (about 90% to 400%, preferably art. Suitable description appears in the patent literature, for about 100-200% of the pore volume). The mixture is option example U.S. Pat. Nos. 4,871,705, 4.937.299, and 5,324,800, ally heated from 30-200° C. during this time. The catalyst EP-A-0418044, EP-A-0591756, WO-A-92/00333 and precursor may be added to this mixture as a Solid, ifa Suitable WO-A-94/O1471. Solvent is employed in the previous step, or as a solution. Or 1544 Mixed catalyst systems can also use non-cyclopen tadienyl, Group 4 or 5 precursor compounds as the additional alternatively, this mixture can be filtered, and the resulting olefin polymerization catalyst. Non-cyclopentadienyl, Group solid mixed with a catalyst precursor solution. Similarly, the 4 or 5 precursor compounds are activable to stable, discrete mixture may be vacuum dried and mixed with a catalyst cationic complexes include those containing bulky, chelating, precursor Solution. The resulting catalyst mixture is then diamide ligands, such as described in U.S. Pat. No. 5.318,935 stirred for 1 minute to 10 hours, and the catalyst is either and “Conformationally Rigid Diamide Complexes: Synthesis filtered from the solution and vacuum dried or evaporation and Structure of Tantalum (III) Alkyne Derivatives'. D. H. alone removes the solvent. McConville, et al. Organometallics 1995, 14, 3154-3156. 1550 Alternatively, the catalyst precursor and activator U.S. Pat. No. 5,318.935 describes bridged and unbridged, may be combined in solvent to form a solution. Then the bis-amido catalyst compounds of Group 4 metals capable of support is added, and the mixture is stirred for 1 minute to 10 C-olefins polymerization. Bridged bis(arylamido) Group 4 hours. The total Solution Volume may be greater than the pore compounds for olefin polymerization are described by D. H. volume of the support, but some embodiments limit the total McConville, et al., in Organometalics 1995, 14, 5478-5480. solution volume below that needed to form a gel or slurry In addition, D. H. McConville, et al, Macromolecules 1996, (about 90% to 400%, preferably about 100-200% of the pore 29, 5241-5243, describe bridged bis(arylamido) Group 4 volume). After stirring, the residual solvent is removed under compounds that are polymerization catalysts for 1-hexene. vacuum, typically at ambient temperature and over 10-16 Cationic Group-3- or Lanthanide olefin polymerization com hours. But greater or lesser times and temperatures are pos plexes are disclosed in U.S. Pat. No. 6,403,773. sible. 1545 Mixed catalyst systems can also use transition metal 1551. The catalyst precursor may also be supported absent catalyst precursors that have a 2+ oxidation state as the addi the activator, in that case, the activator (and co-activator if tional olefin polymerization catalyst. Typical Ni" and Pd* needed) is added to a slurry process liquid phase. For complexes are diimines, see “New Pd(II)- and Ni(II)-Based example, a solution of catalyst precursor may be mixed with Catalysts for Polymerization of Ethylene and C.-Olefins, M. a support material for a period of about 1 minute to 10 hours. Brookhart, et al., J. Am. Chem. Soc., 1995, 117, 6414-6415, The resulting precatalyst mixture may be filtered from the WO96/23010 and WO97/02298. See additionally the related Solution and dried under vacuum, or evaporation alone bis(imino) Group 8 and 9 organometallic compounds removes the solvent. The total, catalyst-precursor-solution described by V. C. Gibson and others in “Novel olefin poly Volume may be greater than the Support's pore Volume, but merization catalysts based on iron and cobalt'. Chem. Com some embodiments limit the total solution volume below that mun., 849-850, 1998. needed to form agel or slurry (about 90% to 400%, preferably 1546 For a review of other potential catalysts used in about 100 to 200% of the pore volume). combination or series with the invention catalysts, see S. D. 1552. Additionally, two or more different catalyst precur Ittel and L. K. Johnson, Chem. Rev. 2000, 1000, 1169 and V. sors may be placed on the same Support using any of the C. Gibson and S. K. Spitzmesser, Chem. Rev. 2003, 103,283. Support methods disclosed above. Likewise, two or more activators or an activator and co-activator may be placed on Supported Catalysts the same Support. 1547. The catalyst compounds of this invention may be 1553 Suitable solid particle supports are typically com placed on a Support. To prepare uniform Supported catalysts, prised of polymeric or refractory oxide materials, each being the catalyst precursor is preferably dissolved in a suitable preferably porous. Any Support material that has an average Solvent and then the resultant solution is applied to or mixed particle size greater than 10 um is suitable for use in this with the support. The term “uniform supported catalyst” invention. Various embodiments select a porous Support means that the catalyst precursor, the activator and or the material. Such as for example, talc, inorganic oxides, inor activated catalyst approach uniform distribution upon the ganic chlorides, for example magnesium chloride and resin Support's accessible Surface area, including the interior pore ous Support materials such as polystyrene, polyolefin or poly Surfaces of porous Supports. Some embodiments of Supported meric compounds or any other organic Support material and catalysts prefer uniform Supported catalysts; other embodi the like. Some embodiments select inorganic oxide materials ments show no such preference. as the Support material including Group-2, -3, -4, -5,-13, or 1548 Supported catalyst systems may be prepared by any -14 metal or metalloid oxides. Some embodiments select the method effective to Support other coordination catalyst sys catalyst Support materials to include silica, alumina, silica tems, effective meaning that the catalyst So prepared can be alumina, and their mixtures. Other inorganic oxides may used for oligomerizing or polymerizing olefin in a heterog serve either alone or in combination with the silica, alumina, enous process. The catalyst precursor, activator, co-activator or silica-alumina. These are magnesia, titania, Zirconia, and if needed, Suitable solvent, and Support may be added in any the like. Lewis acidic materials such as montmorillonite and order or simultaneously. similar clays may also serve as a Support. In this case, the 1549. By one method, the activator, dissolved in an appro Support can optionally double as the activator component. priate solvent such as toluene may be stirred with the support But additional activator may also be used. US 2010/01 13717 A1 May 6, 2010

1554. The support material may be pretreated by any num taining monomer may further be substituted with one or more ber of methods. For example, inorganic oxides may be cal hydrocarbyl groups including but not limited to C to Co cined, chemically treated with dehydroxylating agents such alkyl groups. Additionally two adjacent Substitutions may be as aluminum alkyls and the like, or both. joined to form a ring structure. Preferred aromatic-group 1555. As stated above, polymeric carriers will also be containing monomers contain at least one aromatic structure Suitable in accordance with the invention, see for example the appended to a polymerizable olefinic moiety. Particularly descriptions in WO95/15815 and U.S. Pat. No. 5,427,991. preferred aromatic monomers include styrene, alpha-methyl The methods disclosed may be used with the catalyst com styrene, para-alkylstyrenes, vinyltoluenes, vinylnaphthalene, plexes, activators or catalyst systems of this invention to allyl benzene, and indene, especially styrene, para-methyl adsorb or absorb them on the polymeric Supports, particularly styrene, 4-phenyl-1-butene and allyl benzene. if made up of porous particles, or may be chemically bound 1561 Non aromatic cyclic group containing monomers through functional groups bound to or in the polymer chains. can also be polymerized or oligomerized with the catalyst 1556. The catalyst supports used herein suitably have a systems of the invention. These monomers can contain up to surface area of from 10-700 m/g, a pore volume of 0.1-4.0 30 carbonatoms. Suitable non-aromatic cyclic group contain cc/g and an average particle size of 10-500 um. Some embodi ing monomers preferably have at least one polymerizable ments select a surface area of 50-500 m/g, a pore volume of olefinic group that is either pendant on the cyclic structure or 0.5-3.5 cc/g, or an average particle size of 20-200 um. Other is part of the cyclic structure. The cyclic structure may also be embodiments select a surface area of 100-400 m/g, a pore further substituted by one or more hydrocarbyl groups such volume of 0.8-3.0 cc/g, and an average particle size of 30-100 as, but not limited to. C to Coalkyl groups. Preferred non um. Catalyst supports typically have a pore size of 10-1000 aromatic cyclic group containing monomers include vinylcy Angstroms, alternatively 50-500 Angstroms, or 75-350 Ang clohexane, vinylcyclohexene, cyclopentadiene, cyclopen StromS. tene, 4-methylcyclopentene, cyclohexene, 1557. The catalyst precursors of the invention are gener 4-methylcyclohexene, cyclobutene, vinyladamantane, nor ally deposited on a support at a loading level of 10-100 bornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propyl micromoles of catalyst precursor per gram of Solid Support; norbornene, 5-butylylnorbornene, 5-pentylnorbornene, alternately 20-80 micromoles of catalyst precursor per gram 5-hexylnorbornene, 5-heptylnorbornene, 5-octylnorbornene, of solid support; or 40-60 micromoles of catalyst precursor 5-nonylnorbornene, 5-decylnorbornene, 5-phenylnor per gram of Support. But greater or lesser values may be used bornene, vinylnorbornene, ethylidene norbornene, 5,6-dim provided that the total amount of solid catalyst precursor does ethylnorbornene, 5,6-dibutylnorbornene and the like. not exceed the Support's pore Volume. 1562 Preferred diolefin monomers useful in this invention include any hydrocarbon structure, preferably C to Co. hav Monomers ing at least two unsaturated bonds, wherein at least one, 1558. When activated with a conventional activator, the typically two, of the unsaturated bonds are readily incorpo halogenated metallocene compounds of the invention can be rated into a polymer by either a stereospecific or a non used to polymerize or oligomerize any unsaturated monomer stereospecific catalyst(s). It is further preferred that the diole or monomers. Preferred monomers include C to Coo olefins, fin monomers be selected from alpha-omega-diene preferably C to Coolefins, preferably C to Cao olefins pref monomers (i.e. di-vinyl monomers). More preferably, the erably C to Coolefins, preferably C to Colefins. In some diolefin monomers are linear di-vinyl monomers, most pref embodiments preferred monomers include linear, branched erably those containing from 4 to 30 carbonatoms. Examples or cyclic alpha-olefins, preferably C to Coo alpha-olefins, of preferred dienes includebutadiene, pentadiene, hexadiene, preferably C to Coalpha-olefins, preferably C to Cao alpha heptadiene, octadiene, nonadiene, decadiene, undecadiene, olefins preferably C to Co alpha-olefins, preferably C to dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, Calpha-olefins. Preferred olefin monomers may be one or hexadecadiene, heptadecadiene, octadecadiene, nonadecadi more of ethylene, propylene, butene, pentene, hexene, hep ene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tene, octene, nonene, decene, dodecene, 4-methylpentene-1, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadi 3-methylpentene-1,3,5,5-trimethylhexene-1, and 5-ethyl ene, octacosadiene, nonacosadiene, triacontadiene, particu nonene-1. larly preferred dienes include 1.6-heptadiene, 1.7-octadiene, 1559. In another embodiment the polymer produced 1.8-nonadiene, 1.9-decadiene, 1,10-undecadiene, 1.11 herein is a copolymer of one or more linear or branched C to dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and Co prochiral alpha-olefins or Cs to Coring containing ole low molecular weight polybutadienes (Mw less than 1000 fins or combinations thereof capable of being polymerized by g/mol). Preferred cyclic dienes include cyclopentadiene, either stereospecific and non-stereospecific catalysts. vinylnorbornene, norbornadiene, ethylidene norbornene, Prochiral, as used herein, refers to monomers that favor the divinylbenzene, dicyclopentadiene or higher ring containing formation of isotactic or syndiotactic polymer when polymer diolefins with or without Substituents at various ring posi ized using stereospecific catalyst(s). tions. 1560 Preferred monomers may also include aromatic 1563) Non-limiting examples of preferred polar unsatur group-containing monomers containing up to 30 carbon ated monomers useful in this invention include nitro Substi atoms. Suitable aromatic-group-containing monomers com tuted monomers including 6-nitro-1-hexene; amine Substi prise at least one aromatic structure, preferably from one to tuted OOCS including N-methylallylamine, three, more preferably a phenyl, indenyl, fluorenyl, or naph N-allylcyclopentylamine, and N-allyl-hexylamine; ketone thyl moiety. The aromatic-group-containing monomer fur Substituted monomers including methyl vinyl ketone, ethyl ther comprises at least one polymerizable double bond such vinylketone, and 5-hexen-2-one; aldehyde Substituted mono that after polymerization, the aromatic structure will be pen mers including acrolein, 2.2-dimethyl-4-pentenal, unde dant from the polymer backbone. The aromatic-group con cylenic aldehyde, and 2,4-dimethyl-2,6-heptadienal; alcohol US 2010/01 13717 A1 May 6, 2010 52

Substituted monomers including allyl alcohol, 7-octen-1-ol. In a preferred embodiment the polymer is a homopolymer of 7-octene-1,2-diol, 10-undecen-1-ol, 10-undecene-1,2-diol, any C to C alpha-olefin. Preferably the polymer is a 2-methyl-3-buten-1-ol; acetal, epoxide and or ether substi homopolymer of ethylene or a homopolymer of propylene. In tuted monomers including 4-hex-5-enyl-2,2-dimethyl-1,3 another embodiment the polymer is a copolymer comprising dioxolane, 2,2-dimethyl-4-non-8-enyl-1,3dioxolane, ethylene and one or more of any of the monomers listed acrolein dimethyl acetal, butadiene monoxide, 1.2-epoxy-7- above. In another embodiment the polymer is a copolymer octene, 1.2-epoxy-9-decene, 1.2-epoxy-5-hexene, 2-methyl comprising propylene and one or more of any of the mono 2-vinyloxirane, allyl glycidyl ether, 2.5-dihydrofuran, 2-cy mers listed above. In another preferred embodiment the clopenten-1-one ethylene ketal, 11-methoxyundec-1-ene, homopolymers or copolymers described, additionally com and 8-methoxyoct-1-ene; Sulfur containing monomers prise one or more diolefin comonomers, preferably one or including allyl disulfide; acid and ester Substituted monomers more C to Cao diolefins. including acrylic acid, vinylacetic acid, 4-pentenoic acid, 1566 In another preferred embodiment the polymer pro 2,2-dimethyl-4-pentenoic acid, 6-heptenoic acid, trans-2,4- duced herein is a copolymer of ethylene and one or more C pentadienoic acid, 2,6-heptadienoic acid, methyl acrylate, to Colinear, branched or cyclic monomers, preferably one or ethyl acrylate, tert-butyl acrylate, n-butyl acrylate, meth more C to C linear, branched or cyclic alpha-olefins. Pref acrylic acid, methyl methacrylate, ethyl methacrylate, tert erably the polymer produced herein is a copolymer of ethyl butyl methacrylate, n-butyl methacrylate, hydroxypropyl ene and one or more of propylene, butene, pentene, hexene, acrylate, acetic acidoct-7-enyl ester, non-8-enoic acid methyl heptene, octene, nonene, decene, dodecene, 4-methylpen ester, acetic acid undec-10-enyl ester, dodec-11-enoic acid tene-1,3-methylpentene-1,3,5,5-trimethylhexene-1, cyclo methyl ester, propionic acid undec-10-enyl ester, dodec-11 pentene, 4-methylcyclopentene, cyclohexene, and 4-methyl enoic acid ethyl ester, and nonylphenoxypolyetheroxy acry cyclohexene. late; siloxy containing monomers including trimethyloct-7- 1567. In another preferred embodiment the polymer pro enyloxysilane, and trimethylundec-10-enyloxysilane, polar duced herein is a copolymer of propylene and one or more C functionalized norbornene monomers including 5-nor or C to Colinear, branched or cyclic monomers, preferably bornene-2-carbonitrile, 5-norbornene-2-carboxaldehyde, one or more C or C to C linear, branched or cyclic alpha 5-norbornene-2-carboxylic acid, cis-5-norbornene-endo-2, olefins. Preferably the polymer produced herein is a copoly 3-dicarboxylic acid, 5-norbornene-2.2.-dimethanol, cis-5- mer of propylene and one or more of ethylene, butene, pen norbornene-endo-2,3-dicarboxylic anhydride, 5-nor tene, hexene, heptene, octene, nonene, decene, dodecene, bornene-2-endo-3-endo-dimethanol, 5-norbornene-2-endo 4-methylpentene-1,3-methylpentene-1, and 3.5,5-trimethyl 3-exo-dimethanol, 5-norbornene-2-methanol, 5-norbornene hexene-1. 2-ol. 5-norbornene-2-yl acetate, 1-2-(5-norbornene-2-yl) 1568. In a preferred embodiment, the polymer produced ethyl-3,5,7,9,11,13,15-heptacyclopentylpentacyclo9.5.1. herein is a homopolymer of norbornene or a copolymer of 1.1.17 octasiloxane, 2-benzoyl-5-norbornene, norbornene and a Substituted norbornene, including polar 2-acetyl-5-norbornene, 7-syn methoxymethyl-5-norbornen functionalized norbornenes. 2-one, 5-norbornen-2-ol, and 5-norbornen-2-yloxy-trimeth ylsilane, and partially fluorinated monomers including non 1569. In a preferred embodiment the copolymers afluoro-1-hexene, allyl-1,1,2,2,-tetrafluoroethyl ether, 2.2.3, described herein comprise at least 50 mole% of a first mono 3-tetrafluoro-non-8-enoic acid ethyl ester, 1.1.2.2- mer and up to 50 mole % of other monomers. tetrafluoro-2-(1,1,2,2-tetrafluoro-oct-7-enyloxy)- 1570. In another embodiment, the polymer comprises: ethanesulfonyl fluoride, acrylic acid 2.2.3.3.4.4.5,5,6,6,7,7, 1571 (a) a first monomer present at from 40 to 95 mole 8,8,8-pentadecafluoro-octyl ester, and 1,1,2,2-tetrafluoro-2- %, preferably 50 to 90 mole%, preferably 60 to 80 mole (1,1,2,2,3,3,4,4-octafluoro-dec-9-enyloxy)-ethanesulfonyl %, and fluoride. 1572 (b) a comonomer present at from 5 to 60 mole%, 1564. In an embodiment herein, the process described preferably 10 to 40 mole %, more preferably 20 to 40 herein is used to produce an oligomer of any of the monomers mole 96, and listed above. Preferred oligomers include oligomers of any C 1573 (c) a termonomer present at from 0 to 10 mole%, to Co olefins, preferably C to C2 alpha-olefins, most pref more preferably from 0.5 to 5 mole %, more preferably erably oligomers comprising ethylene, propylene and or 1 to 3 mole %. butene are prepared. A preferred feedstock for the oligomer 1574. In a preferred embodiment the first monomer (a) ization process is the alpha-olefin, ethylene. But other alpha comprises one or more of any C to C linear branched or olefins, including but not limited to propylene and 1-butene, cyclic alpha-olefins, including propylene, butene, (and all may also be used alone or combined with ethylene. Preferred isomers thereof), pentene (and all isomers thereof), hexene alpha-olefins include any C to Cao alpha-olefin, preferably (and all isomers thereof), heptene (and all isomers thereof), any C to Co alpha-olefin, preferably any C to C2 alpha and octene (and all isomers thereof). Preferred monomers olefin, preferably ethylene, propylene, and butene, most pref include propylene, 1-butene, 1-hexene, 1-octene, cyclopen erably ethylene. Dienes may be used in the processes tene, cyclohexene, cyclooctene, hexadiene, cyclohexadiene described herein, preferably alpha-omega-dienes are used and the like. alone or in combination with mono-alpha olefins. 1575. In a preferred embodiment the comonomer (b) com 1565. In a preferred embodiment the process described prises one or more of any C to Cao linear, branched or cyclic herein may be used to produce homopolymers or copolymers. alpha-olefins (provided ethylene, if present, is present at 5 (For the purposes of this invention and the claims thereto a mole % or less), including ethylene, propylene, butene, pen copolymer may comprise two, three, four or more different tene, hexene, heptene, and octene, nonene, decene, undecene, monomer units.) Preferred polymers produced herein include dodecene, hexadecene, butadiene, hexadiene, heptadiene, homopolymers or copolymers of any of the above monomers. pentadiene, octadiene, nonadiene, decadiene, dodecadiene, US 2010/01 13717 A1 May 6, 2010

styrene, 3.5.5-trimethylhexene-1,3-methylpentene-1,4-me conditions. All documents are incorporated by reference for thylpentene-1, cyclopentadiene, and cyclohexene. description of polymerization processes, ionic activators and 1576. In a preferred embodiment the termonomer (c) com useful scavenging compounds. prises one or more of any C to Cao linear, branched or cyclic 1581. The invention catalyst compositions can be used alpha-olefins, (provided ethylene, if present, is present at 5 individually or can be mixed with other known polymeriza mole % or less), including ethylene, propylene, butene, pen tion catalysts to prepare polymer blends. Monomer and cata tene, hexene, heptene, and octene, nonene, decene, undecene, lyst selection allows polymer blend preparation under condi dodecene, hexadecene, butadiene, hexadiene, heptadiene, tions analogous to those using individual catalysts. Polymers pentadiene, octadiene, nonadiene, decadiene, dodecadiene, having increased MWD for improved processing and other styrene, 3.5.5-trimethylhexene-1,3-methylpentene-1,4-me traditional benefits available from polymers made with mixed thylpentene-1, cyclopentadiene, and cyclohexene. catalyst systems can thus be achieved. 1577. In a preferred embodiment the monomers described 1582 Generally, when using invention catalysts, particu above further comprise one or more dienes at up to 10 weight larly when they are immobilized on a Support, the complete %, preferably at 0.00001 to 1.0 weight%, preferably 0.002 to catalyst system will additionally comprise one or more scav 0.5 weight %, even more preferably 0.003 to 0.2 weight%, enging compounds. Here, the term Scavenging compound based upon the total weight of the composition. In some means a compound that removes polar impurities from the embodiments 500 ppm or less of diene is added to the poly reaction environment. These impurities adversely affect cata merization, preferably 400 ppm or less, preferably or 300 lyst activity and Stability. Typically, purifying steps are usu ppm or less. In other embodiments at least 50 ppm of diene is ally used before introducing reaction components to a reac added to the polymerization, or 100 ppm or more, or 150 ppm tion vessel. But such steps will rarely allow polymerization O. O. without using some scavenging compounds. Normally, the polymerization process will still use at least Small amounts of Polymerization Processes Scavenging compounds. 1578 Invention catalyst complexes are useful in polymer 1583 Typically, the scavenging compound will be an izing unsaturated monomers conventionally known to organometallic compound Such as the Group 13 organome undergo metallocene-catalyzed polymerization Such as Solu tallic compounds of U.S. Pat. Nos. 5,153,157, 5,241,025 and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132, and tion, slurry, gas-phase, and high-pressure polymerization. that of WO95/07941. Exemplary compounds include triethyl Typically one or more transition metal compounds, one or aluminum, triethyl borane, tri-iso-butyl aluminum, methyl more activators, and one or more monomers are contacted to alumoxane, iso-butyl alumoxane, and tri-n-octyl aluminum. produce polymer. These catalysts may be Supported and as Those Scavenging compounds having bulky or Co-Co linear such will be particularly useful in the known, fixed-bed, mov hydrocarbyl substituents connected to the metal or metalloid ing-bed, fluid-bed, slurry, solution, or bulk operating modes center usually minimize adverse interaction with the active conducted in single, series, or parallel reactors. catalyst. Examples include triethylaluminum, but more pref 1579. One or more reactors in series or in parallel may be erably, bulky compounds such as tri-iso-butyl aluminum, tri used in the present invention. The transition metal compound, iso-phenylaluminum, and long-chain linear alkyl-substituted activator and when required, co-activator, may be delivered as aluminum compounds, such as tri-n-hexyl aluminum, tri-n- a solution or slurry, either separately to the reactor, activated octyl aluminum, or tri-n-dodecyl aluminum. When alumox in-line just prior to the reactor, or preactivated and pumped as ane is used as the activator, any excess over that needed for an activated solution or slurry to the reactor. Polymerizations activation will scavenge impurities and additional scavenging are carried out in either single reactor operation, in which compounds may be unnecessary. Alumoxanes also may be monomer, comonomers, catalyst/activator/co-activator, added in Scavenging quantities with other activators, e.g., optional Scavenger, and optional modifiers are added continu methylalumoxane, Me HNPhIB(pfp), or B(pfp) where ously to a single reactor or in series reactor operation, in perfluorophenyl-pfp=CFs. which the above components are added to each of two or more 1584 Interms of polymer density, the polymers capable of reactors connected in series. The catalyst components can be production in accordance the invention, can range from about added to the first reactor in the series. The catalyst component 0.85 to about 0.95, preferably from 0.87 to 0.93, more pref may also be added to both reactors, with one component erably 0.89 to 0.920. Polymer molecular weights can range being added to first reaction and another component to other from about 3000 Mn to about 2,000,000 Min or greater. reactors. In one preferred embodiment, the precatalyst is acti Molecular weight distributions can range from about 1.1 to vated in the reactor in the presence of olefin. about 50.0, with molecular weight distributions from 1.2 to 1580 Ethylene-alpha-olefin (including ethylene-cyclic about 5.0 being more typical. Pigments, antioxidants and olefin and ethylene-alpha-olefin-diolefin) elastomers of high other additives, as is known in the art, may be added to the molecular weight and low crystallinity can be prepared uti polymer. lizing the catalysts of the invention under traditional Solution processes or by introducing ethylene gas into a slurry utilizing the alpha-olefin or cyclic olefin or mixture thereof with other Gas Phase Polymerization monomers, polymerizable and not, as a polymerization dilu 1585 Generally, in a fluidized gas bed process used for ent in which the catalyst Suspension is suspended. Typical producing polymers, a gaseous stream containing one or ethylene pressures will be between 10 and 1000 psig (69 more monomers is continuously cycled through a fluidized 6895 kPa) and the polymerization diluent temperature will bed in the presence of a catalyst under reactive conditions. typically be between -10 and 160° C. The process can be The gaseous stream is withdrawn from the fluidized bed and carried out in a stirred tank reactor or a tubular reactor, or recycled backinto the reactor. Simultaneously, polymer prod more than one reactor operated in series or in parallel. See the uct is withdrawn from the reactor and fresh monomer is added disclosure of U.S. Pat. No. 5,001.205 for general process to replace the polymerized monomer. (See for example U.S. US 2010/01 13717 A1 May 6, 2010 54

Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352, in the polymerization medium is typically an alkane having 749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 from 3 to 7 carbon atoms, preferably a branched alkane. The and 5,668,228 all of which are fully incorporated herein by medium employed should be liquid under the conditions of reference.). polymerization and relatively inert. When a propane medium 1586. The reactor pressure in a gas phase process may vary is used the process should be operated above the reaction from about 10 psig (69 kPa) to about 500 psig (3448 kPa), diluent critical temperature and pressure. Preferably, a hex preferably from about 100 psig (690 kPa) to about 500 psig ane or an isobutane medium is employed. (3448 kPa), preferably in the range of from about 200 psig 1593. In one embodiment, a preferred polymerization (1379 kPa) to about 400 psig (2759 kPa), more preferably in technique of the invention is referred to as a particle form the range of from about 250 psig (1724 kPa) to about 350 psig polymerization, or a slurry process where the temperature is (2414 kPa). kept below the temperature at which the polymer goes into 1587. The reactor temperature in the gas phase process Solution. Such technique is well known in the art, and may vary from about 30°C. to about 120°C., preferably from described in for instance U.S. Pat. No. 3,248,179 which is about 60° C. to about 115°C., more preferably in the range of fully incorporated herein by reference. The preferred tem from about 70° C. to 110°C., and most preferably in the range perature in the particle form process is within the range of of from about 70° C. to about 95°C. In another embodiment about 85°C. to about 110°C. Two preferred polymerization when high density polyethylene is desired then the reactor methods for the slurry process are those employing a loop temperature is typically between 70 and 105° C. reactor and those utilizing a plurality of stirred reactors in 1588. The productivity of the catalyst or catalyst system in series, parallel, or combinations thereof. Non-limiting a gas phase system is influenced by the partial pressure of the examples of slurry processes include continuous loop or main monomer. The preferred mole percent of the main stirred tank processes. Also, other examples of slurry pro monomer, ethylene or propylene, preferably ethylene, is from cesses are described in U.S. Pat. No. 4,613,484, which is about 25 to 90 mole percent and the comonomer partial pres herein fully incorporated by reference. sure is in the range of from about 138 kPa to about 517 kPa, 1594. In another embodiment, the slurry process is carried preferably about 517 kPa to about 2069 kPa, which are typical out continuously in a loop reactor. The catalyst, as a slurry in conditions in a gas phase polymerization process. Also in isobutane oras a dry free flowing powder, is injected regularly Some systems the presence of comonomer can increase pro to the reactor loop, which is itself filled with circulating slurry ductivity. of growing polymer particles in a diluent of isobutane con 1589. In a preferred embodiment, the reactor utilized in taining monomer and comonomer. Hydrogen, optionally, the present invention is capable of producing more than 500 may be added as a molecular weight control. The reactor is lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr maintained at a pressure of 3620 kPa to 4309 kPa and at a (90.900 Kg/hr) or higher, preferably greater than 1000 lbs/hr temperature in the range of about 60° C. to about 104°C. (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540 depending on the desired polymer melting characteristics. Kg/hr), even more preferably greater than 25,000 lbs/hr (11, Reaction heat is removed through the loop wall since much of 300 Kg/hr), still more preferably greater than 35,000 lbs/hr the reactor is in the form of a doublejacketed pipe. The slurry (15,900 Kg/hr), still even more preferably greater than 50,000 is allowed to exit the reactor at regular intervals or continu lbs/hr (22,700 Kg/hr) and preferably greater than 65,000 lbs/ ously to a heated low pressure flash vessel, rotary dryer and a hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45.500 nitrogen purge column in sequence for removal of the isobu Kg/hr), and most preferably over 100,000 lbs/hr (45.500 tane diluent and all unreacted monomer and comonomers. Kg/hr). The resulting hydrocarbon free powder is then compounded 1590. Other gas phase processes contemplated by the pro for use in various applications. cess of the invention include those described in U.S. Pat. Nos. 1595. In another embodiment, the reactor used in the 5,627,242, 5,665,818 and 5,677,375, and European publica slurry process of the invention is capable of and the process of tions EP-A-0794 200, EP-A-0 802 202 and EP B-634 421 the invention is producing greater than 2000 lbs of polymer all of which are herein fully incorporated by reference. per hour (907 Kg/hr), more preferably greater than 5000 1591. In another preferred embodiment the catalyst sys lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 tem is in liquid form and is introduced into the gas phase lbs/hr (4540 Kg/hr). In another embodiment the slurry reactor reactor into a resin particle lean Zone. For information on how used in the process of the invention is producing greater than to introduce a liquid catalyst system into a fluidized bed 15,000 lbs of polymer per hour (6804 Kg/hr), preferably polymerization into a particle lean Zone, see U.S. Pat. No. greater than 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 5,693.727, which is incorporated by reference herein. lbs/hr (45.500 Kg/hr). 1596. In another embodiment in the slurry process of the Slurry Phase Polymerization invention the total reactor pressure is in the range of from 400 1592. A slurry polymerization process generally operates psig (2758 kPa) to 800 psig (5516 kPa), preferably 450 psig between 1 to about 50 atmosphere pressure range (15 psig to (3103 kPa) to about 700 psig (4827 kPa), more preferably 500 735 psig, 103 kPa to 5068 kPa) or even greater and tempera psig (3448 kPa) to about 650 psig (44.82 kPa), most preferably tures in the range of 0° C. to about 120° C. In a slurry from about 525 psig (3620 kPa) to 625 psig (4309 kPa). polymerization, a Suspension of Solid, particulate polymer is 1597. In yet another embodiment in the slurry process of formed in a liquid polymerization diluent medium to which the invention the concentration of predominant monomer in monomer and comonomers along with catalyst are added. the reactor liquid medium is in the range of from about 1 to 10 The Suspension including diluent is intermittently or continu weight percent, preferably from about 2 to about 7 weight ously removed from the reactor where the volatile compo percent, more preferably from about 2.5 to about 6 weight nents are separated from the polymerand recycled, optionally percent, most preferably from about 3 to about 6 weight after a distillation, to the reactor. The liquid diluent employed percent. US 2010/01 13717 A1 May 6, 2010

1598. In a further embodiment the process, preferably a olefins and optionally other copolymerizable olefins, the tem slurry or gas phase process, is operated in the absence of or perature of the medium within which the polymerization essentially free of any scavengers, such as triethylaluminum, reaction occurs is at least 120° C. and preferably above 140° trimethylaluminum, tri-iso-butylaluminum and tri-n-hexyla C. and may range to 350° C., but below the decomposition luminum and diethyl aluminum chloride, dibutyl Zinc and the temperature of said polymer product, typically from 310°C. like. This process is described in International Patent Publi to 325° C. Preferably, the polymerization is completed at a cation No. WO96/08520 and U.S. Pat. No. 5,712,352, which temperature within the range of 130° C. to 230° C. The are herein fully incorporated by reference. polymerization is completed at a pressure above 200 bar (20 1599. In another embodiment the process is run with scav MPa), and generally at a pressure within the range of 500 bar engers. Typical scavengers include trimethyl aluminum, tri (50 MPa) to 3500 bar (350 MPa). Preferably, the polymeriza iso-butyl aluminum and an excess of alumoxane or modified tion is completed at a pressure within the range from 800 bar alumoxane. (80 MPa) to 2500 bar (250 MPa). 1600. In a preferred embodiment, hydrogen or other chain 1606 For a medium pressure process, the temperature termination agent (Such as phenylsilane) are added to the within which the polymerization reaction occurs is at least slurry polymerization. 80° C. and typically ranges from 80° C. to 250° C., preferably from 100° C. to 220°C., and should for a given polymer in the Homogeneous, Bulk or Solution Phase Polymerization reactor, be above the melting point of said polymer so as to maintain the fluidity of the polymer-rich phase. The pressure 1601 The catalysts described herein can be used advanta can be varied between 100 and 1000 bar for ethylene geously in homogeneous solution processes. Generally this homopolymers and from 30 bar (3 MPa) to 1000 bar (100 involves polymerization in a continuous reactor in which the MPa), especially 50 bar (5 MPa) to 500 bar (50 MPa) for polymer formed and the starting monomer and catalyst mate processes producing ethylene copolymers containing C to rials Supplied, are agitated to reduce or avoid concentration Co olefins and optionally other copolymerizable olefins. gradients. Suitable processes operate above the melting point 1607. After polymerization and deactivation of the cata of the polymers at high pressures, from 1 to 3000 bar (10-30, lyst, the polymer product can be recovered by processes well 000 MPa), in which the monomeracts as diluent or in solution known in the art. Any excess reactants may be flashed off polymerization using a solvent. from the polymer and the polymer obtained extruded into 1602 Temperature control in the reactor is obtained by water and cut into pellets or other suitable comminuted balancing the heat of polymerization and with reactor cooling shapes. For general process conditions, see the general dis by reactorjackets or cooling coils to cool the contents of the closure of U.S. Pat. Nos. 5,084,534, 5,408,017, 6,127,497, reactor, auto refrigeration, pre-chilled feeds, vaporization of 6.255,410, which are incorporated herein by reference. liquid medium (diluent, monomers or solvent) or combina 1608. In another embodiment this invention relates to: tions of all three. Adiabatic reactors with pre-chilled feeds 1. A process for producing a Substituted metallocene com may also be used. The reactor temperature depends on the pound, the process comprising: catalyst used. In general, the reactor temperature preferably can vary between about 0°C. and about 160° C., more pref (a) providing a first compound represented by the formula (1): erably from about 10°C. to about 140°C., and most prefer AMX, ably from about 40°C. to about 120° C. In series operation, wherein: the second reactor temperature is preferably higher than the M is a transition metal atom having a coordination number of first reactor temperature. In parallel reactor operation, the in selected from Group 3, 4, 5 or 6 of the Periodic Table of temperatures of the two reactors are independent. The pres Elements, or a lanthanide metal atom, or actinide metal atom; sure can vary from about 1 mmHg to 2500 bar (25,000 MPa), A is a monocyclic or polycyclic ligand that is pi-bonded to M preferably from 0.1 bar to 1600 bar (1-16,000 MPa), most and is Substituted with at least one halogen or Sulfonate Sub preferably from 1.0 to 500 bar (10-5000 MPa). stituent directly bonded to any sp carbonatomat a bondable 1603. Each of these processes may also be employed in ring position of the ligand; and single reactor, parallel or series reactor configurations. The each X is, independently, a univalent anionic ligand, or two X liquid processes comprise contacting olefin monomers with are joined and bound to the metal atom to form a metallocycle the above described catalyst system in a suitable diluent or ring, or two X are joined to form a chelating ligand, a diene Solvent and allowing said monomers to react for a sufficient ligand, or an alkylidene ligand; and time to produce the desired polymers. Hydrocarbon solvents (b) reacting said first compound with a transfer-agent which are suitable, both aliphatic and aromatic. Alkanes, such as comprises a hydrocarbyl, Substituted hydrocarbyl, halocar hexane, pentane, isopentane, and octane, are preferred. byl, substituted halocarbyl, silylcarbyl, or germylcarbyl radi 1604. The process can be carried out in a continuous cal capable of replacing said at least one halogen or Sulfonate stirred tank reactor, batch reactor, or plug flow reactor, or Substituent of said first compound under reaction conditions. more than one reactor operated in series or parallel. These 2. The process of paragraph 1 wherein A comprises a Substi reactors may have or may not have internal cooling and the tuted monocyclic arenyl ligand or a Substituted polycyclic monomer feed may or may not be refrigerated. See the gen arenyl ligand. eral disclosure of U.S. Pat. No. 5,001.205 for general process 3. The process of paragraph 1 wherein A includes one or more conditions. See also, International Patent Publication Nos. ring heteroatoms selected from boron, a Group 14 atom that is WO 96/33227 and WO 97/22639. not carbon, a Group 15 atom, and a Group 16 atom. 4. The process of paragraph 1 wherein said A is a Substituted Medium and High Pressure Polymerizations cyclopentadienyl, Substituted heterocyclopentadienyl, Sub 1605. In the high pressure process for the polymerization stituted indenyl, substituted heteroindenyl, substitutedifluo of ethylene alone or in combination with Cs to Co alpha renyl, substituted heterofluorenyl, substituted cyclopen US 2010/01 13717 A1 May 6, 2010 56 tanaphthyl, Sub stitutedhetero cyclopentanaphthyl, NR' CR'—CR', RCR'C NR CRCR's RC substituted heterophenyl, substituted hetero cyclopentapen P—CR', RC PR CR' O, S, Se, Te, NR", PR, AsR', talenyl, substituted hetero cyclopentaindenyl, or substituted SbR', O O, S. S. RN NR', RP PR', O S, O NR', heterobenzocyclopentaindenyl ligand. O PR', S NR', S PR', and RN PR' where R is hydro 5. A process for producing a Substituted metallocene com gen or a C-C containing hydrocarbyl, Substituted hydro pound, the process comprising: carbyl, halocarbyl, substituted halocarbyl, silylcarbyl or ger (a) providing a first compound represented by the formula (2): mylcarbyl substituent and optionally two or more adjacent R' may join to form a substituted or unsubstituted, Saturated, partially unsaturated or aromatic, cyclic or polycyclic Sub stituent. 10. The process of any of paragraphs 5 to 8 whereiny is 1 and Q is selected from the group consisting of CH, CH2CH2. wherein CH(CH), SiMe. SiPh. SiMePh, Si(CH), Si(CH), O, S, M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanide NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, and PBu, metal atom, or actinide metal atom; where Me is methyl, Phis phenyl, Et is ethyl, Pr is propyl, and each of J and E is independently a substituted or unsubsti Bu is butyl. tuted, monocyclic or polycyclic ligand pi-bonded to M, 11. A process for producing a Substituted metallocene com wherein at least one of J and E includes at least one halogen or pound, the process comprising: sulfonate substituent directly bonded to an sp carbonatomat (a) providing a first compound represented by the formula (3): a bondable ring position of the ligand; Q is an optional bridging group that is bonded to E and J. and Z X is present when y is one and absent wheny is Zero; o,'R N//N y is Zero or one; and X each X is, independently, a univalent anionic ligand, or two X are joined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and wherein (b) reacting said first compound with a transfer-agent which M is a Group 3, 4, 5 or 6 transition metal atom, or a lanthanide comprises a hydrocarbyl, Substituted hydrocarbyl, halocar metal atom, or actinide metal atom; byl, substituted halocarbyl, silylcarbyl, germylcarbyl radical Z is a Substituted or unsubstituted, monocyclic or polycyclic capable of replacing said at least one halogen or sulfonate ligand that is pi-bonded to M: Substituent of said first compound under reaction conditions Q' is an optional bridging group that is bonded to Zand T, and in the presence of a coupling catalyst. is present when y is one and absent wheny is Zero; 6. The process of paragraph 5 wherein at least one of J and E y is Zero or one; and comprises a Substituted or unsubstituted, monocyclic or poly T is a heteroatom with a coordination number of three from cyclic arenyl ligand. Group 15 or with a coordination number of two from Group 7. The process of paragraph 5 wherein at least one of J and E 16 of the Periodic Table of Elements; includes one or more ring heteroatoms selected from boron, a R" is selected from a C-C substituted or unsubstituted Group 14 atom that is not carbon, a Group 15 atom, and a monocyclic or polycyclic ring structure Substituent that is Group 16 atom. 8. The process of paragraph 5 wherein each of J and E is partially unsaturated, unsaturated or aromatic; or a C-Coo independently a Substituted or unsubstituted cyclopentadi Substituted or unsubstituted, unsaturated or partially unsatur enyl ligand, a Substituted or unsubstituted heterocyclopenta ated, linear or branched alicyclic hydrocarbyl substituent; or dienyl ligand, a Substituted or unsubstituted indenyl ligand, a a C-Coo Substituted or unsubstituted Saturated hydrocarbyl substituted or unsubstituted heteroindenyl ligand, or a substi radical; tuted or unsubstituted fluorenyl ligand, a substituted or t is the coordination number of the heteroatom T (2 or 3) unsubstituted heterofluorenyl ligand, and a substituted or where “t-1-y’ indicates the number of R" substituents bonded unsubstituted cyclopentanaphthyl, or a Substituted or unsub to T; and stituted heterocyclopentanaphthyl ligand, or a Substituted or each X is, independently, a univalent anionic ligand, or two X unsubstituted heterophenyl ligand, or a Substituted or unsub are joined and bound to the metal atom to form a metallocycle stituted heterocyclopentapentalenyl ligand, or a substituted or ring, or two X are joined to form a chelating ligand, a diene unsubstituted heterocyclopentaindenyl ligand, or a Substi ligand, or an alkylidene ligand; tuted or unsubstituted heterobenzocyclopentaindenyl ligand. provided that Z is substituted with at least one halogen or 9. The process of any of paragraphs 5 to 8 whereiny is 1 and sulfonate substituent directly bonded to any sp carbon atom Q is selected from the group consisting of: P(=S)R', P(=Se) at a bondable ring position of the ligand Z, or that R" is R', P(=O)R', RC, R'Si, R'Ge. RCCR', RCCRCR', substituted with at least one halogen or sulfonate substituent RCCR'CR'CR', RC—CR', RC–CR'CR', bonded to an sp carbon atom, or both. RCCR'—CR'CR', R'C—CR'CR'—CR', (b) reacting said first compound with a transfer-agent which R'C—CR'CR'CR', RCSiR, RSiSiR, RCSiR'CR', comprises a hydrocarbyl, Substituted hydrocarbyl, halocar R'SiCR'SiR' R'C—CR'SiR, RCGeR', R'GeGeR', byl, substituted halocarbyl, silylcarbyl, germylcarbyl radical capable of replacing said at least one halogen or Sulfonate Substituent of said first compound under reaction conditions in the presence of a coupling catalyst. 12. The process of paragraph 11 wherein Z comprises a monocyclic or polycyclic arenyl ligand. 13. The process of paragraph 11 wherein Z includes one or more ring heteroatoms selected from boron, a Group 14 atom that is not carbon, a Group 15 atom, and a Group 16 atom. US 2010/01 13717 A1 May 6, 2010 57

14. The process of paragraph 11 wherein Z is independently 24. The process of any preceding paragraphs 1 to 23 wherein a Substituted or unsubstituted cyclopentadienyl ligand, a Sub the halogen substituent is a chloro or bromo substituent. stituted or unsubstituted heterocyclopentadienyl ligand, a 25. The process of any preceding paragraphs 1 to 24 wherein substituted or unsubstituted indenyl ligand, a substituted or M is titanium, Zirconium or hafnium. unsubstituted heteroindenyl ligand, or a substituted or unsub 26. The process of any preceding paragraphs 1 to 25 wherein stituted fluorenyl ligand, a substituted or unsubstituted heter the transfer-agent is an organometallic compound. ofluorenyl ligand, and a Substituted or unsubstituted cyclo 27. The process of paragraph 26 wherein the metal of the pentanaphthyl, or a Substituted or unsubstituted organometallic compound is selected from boron, tin, copper, heterocyclopentanaphthyl ligand, or a Substituted or unsub magnesium, Zinc, aluminum, lithium and Zirconium. stituted heterophenyl ligand, or a substituted or unsubstituted 28. A substituted metallocene compound prepared by the heterocyclopentapentalenyl ligand, or a substituted or unsub process of any preceding paragraphs 1 to 27. stituted heterocyclopentaindenyl ligand, or a Substituted or 29. A catalyst system comprising the Substituted metallocene unsubstituted heterobenzocyclopentaindenyl ligand. compound of paragraph 28 and an activator. 15. The process of any one of paragraphs 11 to 13 wherein 30. A process for polymerizing olefins comprising contacting t-1-y is equal to 1. a metallocene compound prepared by the process of any of 16. The process of any one of paragraphs 11 to 15 wherein T paragraphs 1 to 27 with an activator and at least one olefin. is nitrogen. 31. The process of paragraph 30 wherein said at least one 17. The process of any one of paragraphs 11 to 16 wherein R" olefin comprises ethylene and/or propylene. is selected from methyl, ethyl, all propyl isomers, all butyl isomers, phenyl, benzyl, phenethyl, 1-adamantyl, cyclodode EXPERIMENTAL cyl, cyclohexyl and norbornyl. Synthesis 18. The process of any one of paragraphs 11 to 17 wherein the halogen or sulfonate substituent is on R", and R" is selected 1609 All manipulations with air and moisture sensitive from the group consisting of 2-bromophenyl, 3-bromophe compounds were performed either in an atmosphere of thor nyl, 4-bromophenyl, 2,6-diisopropyl-4-bromophenyl, 2.6- oughly purified argon using a standard Schlenktechnique or dimethyl-4-bromophenyl, 2,4,6-trimethyl-3-bromophenyl, in a controlled atmosphere Glove Box (Vacuum Atmospheres 2-bromo-4,6-dimethylphenyl, 2-bromo-4-methylphenyl, Co.). Tetrahydrofuran (THF, Merck-Merck KGaA, Darms 2-bromo-3,4,6-trimethylphenyl, 2-bromo-4-fluorophenyl, tadt, Germany) and diethyl ether (Merck) were purified by 2-bromo-4,6-difluorophenyl, 2,6-dibromophenyl, 2,6-di distillation over LiAlH, and stored over sodium benzophe bromo-4-methylphenyl, 2,6-dibromo-4-fluorophenyl, 2,5-di none ketyl under an inert atmosphere; prior to use, the sol bromophenyl, and 2,4-dibromophenyl. vents were distilled from the benzophenone ketyl. Hydrocar 19. The process of any one of paragraphs 11 to 18 whereiny bon solvents such as benzene (Merck), toluene (Merck), and is 1 and Q is selected from the group consisting of: P(=S)R', hexanes (Merck) and including benzene-d (Cambridge Iso P(=Se)R', P(=O)R', RC, R,Si, R'Ge. RCCR', tope Laboratories, Inc., for NMR measurements) were typi RCCR'CR', RCCRCR'CR', R'C—CR', cally distilled over CaFI, and were stored over Na/K alloy RC–CR'CR, RCCR'—CR'CR, RC–CRCR'—CR', under an inert atmosphere; prior to use, the solvents were R'C–CR'CR'CR', RCSiR', R'SiSiR', RCSiR'CR', distilled from the Na/K alloy. Methylene chloride (Merck) R'SiCR'SiR' R'C—CR'SiR, RCGeR', R'GeGeR', (and CC1D, for NMR measurements, Cambridge Isotope RC GeR'CR, R'GeCR'GeR', RSiGeR', Laboratories, Inc.) was distilled and stored over CaFI under R'C–CR'GeR', RB, RC BR", RC BR CR', an inert atmosphere; prior to use, the solvent was distilled R'C O CR's RCRC O CRCR, RC O— from the CaFI. Chloroform-d (Merck) was distilled over CR'CR's RC O CR'—CR', RC S CR', PO (Merck) and stored over molecular sieves (3 A). R'CR'C S CR'CR', RC S CR'CR', RC S Thiophene (Merck), 2-methylthiophene (Fluka Chemical CR'—CR', RC Se CR's RCRC Se CR'CR', Corp.-Fluka), furan (Merck), 2-methylfuran RC Se CRCR', RC Se CR'—CR', RC (Aldrich-Aldrich Chemical Co.), benzothiophene (Aldrich), N=CR', RC NR' CR's RC NR' CR'CR's RC benzofuran (Aldrich), 2.0 M "BuLi in hexanes NR' CR'—CR', RCR'C NR' CRCR's RC (Chemetall-Chemetall Chemical Products), 2.0 M4-tert-bu P—CR', and RC PR CR', where R is hydrogen or a tylbromophenylmagnesium bromide in ether (Aldrich), 2.0 C-C containing hydrocarbyl, Substituted hydrocarbyl, M methylzinc chloride in THF (Aldrich), 1.0 M phenylmag halocarbyl, substituted halocarbyl, silylcarbyl or germylcar nesium bromide in THF (Aldrich), 1.0 M p-tolylmagnesium byl substituent and optionally two or more adjacent R may bromide in THF (Aldrich), 1.0M m-tolylmagnesium chloride join to forma Substituted or unsubstituted, saturated, partially in THF (Aldrich), 0.5 M dimethylaminophenylmagnesium unsaturated or aromatic, cyclic or polycyclic Substituent bromide in THF (Aldrich), 1.0 M 2-methoxyphenylmagne 20. The process of any one of paragraphs 11 to 18 whereiny sium bromide in THF (Aldrich), 4-bromobiphenyl (Aldrich), is 1 and Q' is selected from the group consisting of CH, mesityl bromide (Acros Acros Organics), 2-bromotoluene (Acros), 2-bromoanisole (Acros), 3-bromobenzotrifluoride CHCH, CH(CH), SiMe. SiPh. SiMePh, Si(CH), and (Acros), 4-fluorobromobenzene (Acros), 1-bromonaphtha Si(CH), where Me is methyl, and Ph is phenyl. lene (Acros), lithium bis(trimethylsilyl)amide (Aldrich), sty 21. The process of any one of paragraphs 5 to 10 whereiny is rene (Acros), 4-fluorostyrene (Aldrich), NaBPha (Acros), 1 and Q is a bridging group containing at least one Group 13. n-butyl vinyl ether (Acros), 0.5 M ZnCl2 in THF (Aldrich), 14, 15, or 16 element. and Pd(PBus) (Strem=Strem Chemical Co.), dibromobis 22. The process of any one of paragraphs 11 to 20 whereiny (triphenylphosphine)nickel(II) (Aldrich), 2,5-dimethylphe is 1 and Q' is a bridging group containing boron or a Group 14. nylmagnesium bromide (0.5 M in THF, Aldrich), and 4-bi 15 or 16 element. phenylmagnesium bromide (0.5 M in THF, Aldrich) were 23. The process of any preceding paragraphs 1 to 22 wherein used as obtained. Solutions of Grignard reagents (4-phe the halogen or Sulfonate Substituent is a chloro, bromo, iodo, nylphenylmagnesium bromide, 4-tert-butylphenylmagne tosylate or triflate substituent. sium bromide, 2-methylphenylmagnesium bromide, mesityl US 2010/01 13717 A1 May 6, 2010 magnesium bromide, 4-fluorophenylmagnesium bromide, 1626) dimethylsilyl(m-tetramethylcyclopentadienyl)(m- 3-trifluoromethylphenylmagnesium bromide, 2-tolylmagne 4-bromophenylamido)Zirconium dichloride (14), sium bromide, and 1-naphthylmagnesium bromide) in THF 1627 rac-dimethylsilyl-bis(m-4-bromo-6-isopropyl-2- were obtained from magnesium turnings (Aldrich) and the methylinden-1-yl)Zirconium dichloride (15), respective arylbromides in THF at reflux. Trichloromethylsi 1628 rac-dimethylsilyl-bis(m-3-bromo-2,5-dimethylcy lane (Merck) was distilled in the presence of quinoline in clopentab thien-6-yl)Zirconium dichloride (16), argon to eliminate HC1. Celite 503 (Fluka) was dried in vacuum for 20 hour at 200° C. 1629 dimethylsilyl(m-2-methyl-4-bromoinden-1-yl) 1610 "H and 'C NMR spectra were recorded with a (m-tert-butylamido)titanium dichloride (17), Varian VXR400 or Brucker DPX-300 for 0.1-5% solutions in 1630) dimethylsilyl(m-4,5-dimethylcyclopentablthien deuterated solvents. Chemical shifts for "H and C were 6-yl)(m-4-bromo-2,6-dimethylphenylamido)titanium measured relative to TMS. In H NMR spectra, the assign dichloride (18), ment was made on the evidence of double resonance and 1631 rac-dimethylsilyl-bis(m-4-bromo-2,6-dimethylin NOE experiments. C, H microanalyses were done using den-1-yl)Zirconium dichloride (19), CHN O-Rapid analyzer (Heracus). 1632 dimethylsilyl(m-tetramethylcyclopentadienyl)(m- 1611. The synthesis of the halogen substituted catalyst 4-bromophenylamido)titanium dichloride (20), precursors listed below are disclosed in our copending U.S. 1633 dimethylsilyl(m-tetramethylcyclopentadienyl)(m- patent application Ser. Nos. 11/302.798, 11/300,240, 11/300, 4-bromo-2,6-diisopropylphenylamido)titanium dichloride 032 (now U.S. Pat. No. 7,557,171), 11/300.0029 (now U.S. Pat. No. 7,538,168), 11/300,054 (now U.S. Pat. No. 7,446, (21), 216), 11/302,381 (now U.S. Pat. No. 7,550,544) all filed 1634 rac-diethylsilyl-bis(m-4-bromo-2-methylinden-1- concurrently herewith and all incorporated herein by refer yl)Zirconium dichloride (22), ence, and were used to prepare the catalysts listed on Table 1, 1635 dimethylsilyl(m-tetramethylcyclopentadienyl)(m- using the indicated cross-coupling reaction: 4-bromo-2,6-dimethylphenylamido)Zirconium dichloride 1612 (m-2-methyl-4-bromoindenyl)(m-pentamethylcy (23), clopentadienyl)Zirconium dichloride (1), 1636) dimethylsilyl(m-4,5-dimethylcyclopentablthien 1613) (m-2-methyl-4-bromoindenyl)(m-pentamethylcy 6-yl)(m-4-bromo-2,6-dimethylphenylamido)zirconium clopentadienyl)hafnium dichloride (2), dichloride (24), 1614 (m-2-methyl-4-bromoindenyl)(m-cyclopentadi (1637 dimethylsilyl(m-4,5-dimethylcyclopentablthien enyl)Zirconium dichloride (3), 6-yl)(m-4-bromo-2,6-diisopropylphenylamido)Zirco (1615) mixture of d-?l- and meso-bis(m-2-methyl-4-bro nium dichloride (25), moindenyl)Zirconium dichlorides (4), 1638 dimethylsilyl(m-4,5-dimethylcyclopentablthien 1616 bis(m-2-bromoindenyl)Zirconium dichloride (5), 6-yl)(m-4-bromo-2,6-diisopropylphenylamido)titanium 1617 (m-3-bromo-5-methylcyclopentablthienyl)(m- dichloride (26), pentamethylcyclopentadienyl)Zirconium dichloride (6), (1639 4,4'-tolylazandiyl-bis(m-7-bromo-2-methylinde 1618 mixture of d-?l- and meso-bis(m-3-bromo-5-meth nyl)Zirconium dichloride (27), ylcyclopentab thienyl)Zirconium dichlorides (7), 1619 rac-dimethylsilyl-bis(m-4-bromo-2-methylinden 1640 4,4'-oxadiyl-bis(m-7-bromo-2-methylindenyl)Zir 1-yl)Zirconium dichloride (rac-8), conium dichloride (28), 1620 meso-dimethylsilyl-bis(m-4-bromo-2-methylin 1641 (m-4-bromo-6-chloroindenyl)(m-pentamethylcy den-1-yl)Zirconium dichloride (meso-8), clopentadienyl)Zirconium dichloride (29), 1621 rac-dimethylsilyl-bis(m-3-bromo-5-methylcyclo (1642 rac-dimethylsilyl-bis(m-4-bromo-2-isopropylin pentabthien-6-yl)Zirconium dichloride (rac-9), den-1-yl)Zirconium dichloride (30), 1622 4,4'-sulfandiyl-bis(m-7-bromo-2-methylindenyl) 1643) isopropylidene-(m-4-bromo-3-methylinden-1-yl) Zirconium dichloride (10), (m-cyclopentadienyl)zirconium dichloride (31), 1623 dimethylsilyl(m-2-methyl-4-bromoinden-1-yl)- 1644 isopropylidene-(m-2,7-dibromofluoren-9-yl)(m- (m-tert-butylamido)Zirconium dichloride (11), cyclopentadienyl)Zirconium dichloride (32), 1624) dimethylsilyl(m-tetramethylcyclopentadienyl)(m- 1645) dimethylsilyl(m-tetramethylcyclopentadienyl)(m- 4-bromo-2,6-diisopropylphenylamido)Zirconium dichlo 4-bromo-2,6-dimethylphenylamido)titanium dichloride ride (12), (33), and 1625 rac-dimethylsilyl-bis(m-4-bromo-2,5-dimethylin 1646 (m-4,7-dibromoinden-1-yl)(m-pentamethylcyclo den-1-yl)Zirconium dichloride (13), pentadienyl)Zirconium dichloride (34).

TABLE 1. Precatalyst Prepared from Halogen-Substituted Metallocenes

Ex. Prec. Precatalyst Rxn (m-2,4-di-Me-indenyl)(m-MesCp)ZrCl (1a) N (m-2-Me-4-Ph-indenyl)(m-Me-Cp)ZrCl (1b) N (m-2-Me-4-Ph-indenyl)(n-MesCp)ZrCl (1b) S (m-2-Me-4-(4-MeCH)-indenyl)(m-Me-Cp)ZrCl N (1c) 1 (m-2-Me-4-(3-MeCH)-indenyl)(n-MesCp)ZrCl N (1d)

US 2010/01 13717 A1 May 6, 2010 64

1647 Examples showing how these cross-coupling reac 1651 Anal. calc. for CHC17r: C, 57.25; H, 5.95. tions were carried out follow. Found: C, 57.30; H, 5.99. 1652 H NMR (CD): 8 6.99 (m. 1H, 5-H in indenyl), Examples 1a-lp 6.90 (m. 1H, 7-H in indenyl), 6.82 (dd, J=8.2 Hz, J=6.7 Hz, 1H, 6-H in indenyl), 6.54 (m. 1H, 1-H in indenyl), 5.57 (d. Negishi coupling applying (m-2-methyl-4-bromoin J=2.2 Hz, 1H, 3-H in indenyl), 2.43 (s.3H, 4-Mein indenyl), denyl)(m-pentamethylcyclopentadienyl)Zirconium 2.05 (s3H, 2-Me in indenyl), 1.77 (s, 15H, CMs). dichloride (1) 1653) 'C{H} NMR (CD): & 135.7, 1348, 1324, 125. 1648 4, 125.2, 124.6, 120.9, 119.1, 111.1, 100.9, 20.1, 16.8, 12.7. Example 1c Br (m-2-methyl-4-p-tolylindenyl)(m-pentamethylcy clopentadienyl)Zirconium dichloride (1c) 1654. In a 16 ml vial equipped with a PTFE coated stir bar, RZnCl 0.79 ml of 1.0 M (0.79 mmol) p-tolylmagnesium bromide in Cl Pd(PBus) THF was added by a dosing pipette to a mixture of 1.73 ml of 0.5 M (0.87 mmol) ZnCl in THF and 5 ml of THF by vigor 3.1, THF ous stirring at ambient temperature. This organozinc reagent was additionally stirred for 1 hour and then added to a mixture of 306 mg (0.61 mmol) of 1, 0.61 ml of 0.02 M(0.012 mmol) Pd(P'Bus), in THF, and 2 ml of THF placed in a separate 16 1 ml vial equipped with a PTFE coated stir bar. The reaction R mixture was stirred for 4 hours at room temperature and then evaporated to dryness. To the residue, a solution of 1.0 ml of MeSiCl, in 10 ml of dry dichloromethane was added to elimi nate an excess of the organozinc reagent. The resulting mix ture was stirred at ambient temperature for 1 hour and then G- Zr -Cl evaporated to dryness. In order to eliminate THF contamina tion, the residue was treated with hot toluene (20 ml). The 61 NC Suspension was evaporated to dryness. The residue was addi tionally treated with 60 ml of hot toluene, and the suspension formed was filtered through Celite 503. The toluene extract was evaporated to dryness. The obtained solid was washed 1a-1p with 3x15 ml of hexanes and dried in vacuum. Yield 261 mg (83%) of yellowish solid. 1649 R=Me (1a), CHs (1b), 4-MeCH (1c), 3-MeCH 1655 Anal. calc. for CHC17r: C, 62.77: H, 5.85. (1d), 2-MeCH (1e), 4-TBuCH (1f), 4-FC.H. (1g), Found: C, 62.86; H, 5.92. 3-CFCH (1h), 2-MeOCH (1i), 4-biphenyl (1k), 1-naph 1656) "HNMR (CDC1): 87.54 (m,2H,3,5-Hinp-tolyl), thyl (11), 2-thienyl (1 m), 2-benzothienyl (1n), 2-furyl (1o), 7.31 (dt, J–8.4 Hz, J=0.9 HZ, 1H, 7-H in indenyl), 7.24 (m, 2-benzofuryl (1p). 2H, 2,6-H in p-tolyl), 7.21 (dd, J–7.0 Hz, J=0.9 HZ, 1H, 5-H in indenyl), 7.07 (dd, J–8.4 Hz, J–7.0 Hz, 1H, 6-Hin indenyl), Example la 6.69 (m. 1H, 1-H in indenyl), 6.19 (m. 1H, 3-H in indenyl), 2.37 (s, 3H, 4-Me in p-tolyl), 2.15 (s, 3H, 2-Me in indenyl), (m-2,4-dimethylindenyl)(m-pentamethylcyclopen 1.97 (s, 15H, CMes). tadienyl)Zirconium dichloride (1a) 1657 C{H} NMR (CDC1): 8 139.2, 139.1, 138.5, 1650. In a 16 ml vial equipped with a PTFE coated stir bar, 133.6, 132.4, 130.7, 130.2, 126.9, 126.6, 126.4, 122.3, 115.7, to a suspension of 300 mg (0.59 mmol) of 1 in 8.0 ml of THF, 107.3, 102.3, 22.5, 17.3, 13.9. 0.39 ml of 2.0 M MeZnC1 (0.78 mmol) in THF and 0.59 ml of 0.02 M (0.012 mmol) Pd(PBus), in THF were added by a Example 1 c' dosing pipette. The reaction mixture was stirred for 4 hours at (m-2-methyl-4-p-tolylindenyl)(m-pentamethylcy room temperature and then evaporated to dryness. To the clopentadienyl)Zirconium dichloride (1c) residue, a solution of 1.0 ml of MeSiCl, in 10 ml of dry dichloromethane was added to eliminate an excess of the 1658. In a 16 ml vial equipped with a PTFE coated stir bar, organozinc reagent. The resulting mixture was stirred at 0.79 ml of 1.0 M (0.79 mmol) p-tolylmagnesium bromide in ambient temperature for 1 hour and then evaporated to dry THF was added by a dosing pipette to a mixture of 1.73 ml of ness. In order to eliminate THF contamination, the residue 0.5 M (0.87 mmol) ZnCl in THF and 5 ml of THF by vigor was treated with hot toluene (20 ml), then, the suspension was ous stirring at ambient temperature. This organozinc reagent evaporated to dryness. The residue was additionally treated was additionally stirred for 1 hour and then added to a mixture with 60 ml of hot toluene, and the resulting Suspension was of 306 mg (0.61 mmol) of 1.9 mg (0.012 mmol) of NiBr, filtered through Celite 503. The toluene extract was evapo (PPh), and 3 ml of THF placed in a separate 16 ml vial rated to dryness. The obtained solid was washed with 3x15 ml equipped with a PTFE coated stir bar. The reaction mixture of hexanes and dried in vacuum. Yield 144 mg (54%) of was stirred for 48 hours at room temperature and then evapo yellowish solid. rated to dryness. To the residue, a solution of 1.0 ml of US 2010/01 13717 A1 May 6, 2010

MeSiC1 in 10 ml of dry dichloromethane was added to elimi 1667 ''C{H} NMR (CDC1,): & 142.6, 140.3, 134.7, nate an excess of the organozinc reagent. The resulting mix 133.7, 131.5, 131.2, 130.3, 128.1, 128.0, 127.7, 123.8, 123.7, ture was stirred at ambient temperature for 1 hour and then 116.9, 103.6, 18.5, 15.1. evaporated to dryness. In order to eliminate THF contamina tion, the residue was treated with hot toluene (20 ml). The Example 1d Suspension was evaporated to dryness. The residue was addi tionally treated with 60 ml of hot toluene, and the suspension (m-2-methyl-4-m-tolylindenyl)(m-pentamethylcy formed was filtered through Celite 503. The toluene extract clopentadienyl)Zirconium dichloride (1 d) was evaporated to dryness. The obtained solid was washed 1668. Following the procedure described for 1 c, 0.90 ml of with 3x15 ml of hexanes and dried in vacuum. Yield 277 mg 1.0 M (0.90 mmol) m-tolylmagnesium chloride in THF, 1.98 (88%) of yellowish solid of 1c. Hand 'C{H} NMR spectra ml of 0.5 M (0.99 mmol) ZnCl2 in THF, 350 mg (0.69 mmol) were identical to those for the sample obtained in the example of 1, and 0.69 ml of 0.02 M (0.014 mmol) Pd(PBus) in THF 1c above. gave yellowish solid. Yield 272 mg (76%). 1659 Anal. calc. for CHC17r: C, 62.77; H, 5.85. 1669 Anal. calc. for CHC17r: C, 62.77; H, 5.85. Found: C, 62.86; H, 5.92. Found: C, 62.95; H, 6.00. 1670 "H NMR (CDC1): 8 727-7.48 (m, 4H, 2,4,5,6-H Example 1b in m-tolyl), 7.22(dd, J=7.1 Hz, J=1.0Hz, 1H, 5-Hin indenyl), 7.16 (m, 1H, 7-H in indenyl), 7.07 (dd, J=8.4 Hz, J=7.1 Hz, (m-2-methyl-4-phenylindenyl)(m-pentamethylcy 1H, 6-H in indenyl), 6.70 (m. 1H, 1-H in indenyl), 6.20 (d. clopentadienyl)Zirconium dichloride (1b) J=2.2 HZ, 1H, 3-H in indenyl), 2.38 (s.3H, 3-Meim m-tolyl), 2.15 (s.3H, 2-Mein indenyl), 1.97 (s, 15H, CMes). 1660. Following the procedure described for 1 c, 0.90 ml of 1.0 M (0.90 mmol) phenylmagnesium bromide in THF, 1.98 Example le ml of 0.5M (0.99 mmol) ZnCl, in THF, 350 mg (0.69 mmol) (m-2-methyl-4-o-tolylindenyl)(m-pentamethylcy of 1, and 0.69 ml of 0.02 M (0.014 mmol) Pd(P'Bus) in THF clopentadienyl-m)zirconium dichloride (1e) gave yellowish solid. Yield 290 mg (83%). 1661 Anal. calc. for CHCl2r: C, 62.13; H, 5.61. 1671. Following the procedure described for 1 c, 0.59 ml of Found: C, 62.34; H, 5.71. 0.83 M (0.49 mmol) o-tolylmagnesium bromide in THF, 1.08 1662) H NMR (CDC1): 8 7.62-7.69 (m, 2H, 2,6-H in ml of 0.5 M (0.54 mmol) ZnCl2 in THF, 190 mg (0.38 mmol) Ph), 7.28-7.47 (m, 4H, 7-Hin indenyland 3,4,5-H in Ph), 7.23 of 1, and 0.38 ml of 0.02 M (0.008 mmol) Pd(PBus), in THF (dd, J–7.0 Hz, J=0.9 HZ, 1H, 5-H in indenyl), 7.08 (dd, J–8.5 gave yellowish solid. Yield 150 mg (77%). HZ, J=7.0 Hz, 1H, 6-H in indenyl), 6.70 (m, 1H, 1-H in 1672 Anal. calc. for CHC17r: C, 62.77: H, 5.85. indenyl), 6.21 (d. J=2.3 Hz, 1H, 3-H in indenyl), 2.05 (s.3H, Found: C, 62.85; H, 5.97. 2-Mein indenyl), 1.88 (s, 15H, CMs). 1673 H NMR (CDC1): 8 7.65 (brs, 1H, 5-H in inde nyl), 7.32 (m. 1H, 7-H in indenyl), 7.16-7.27 (m,3H,3,4,5-H 1663) 'C{H} NMR (CDC1,): & 142.6, 140.3, 134.7, in o-tolyl), 7.03-7.14 (m. 2H, 6-H in indenyl and 6-H in 133.7, 131.5, 131.2, 130.3, 128.1, 128.0, 127.7, 123.8, 123.7, o-tolyl), 6.28 (bris, 1H, 1-H in indenyl), 6.19 (d. J=2.3 Hz, 1H, 116.9, 103.6, 18.5, 15.1. 3-H in indenyl), 2.13 (s, 3H, 2-Me in o-tolyl), 2.02 (s, 3H, 2-Me in indenyl), 1.98 (s, 15H, CMes). Examples 1b2 1674 'C{H} NMR (CDC1,): & 138.3, 137.6, 1374, 131.7 (brs), 131.5, 1314, 130.8, 130.6, 129.7, 129.0, 128.7, Suzuki-Miyaura reaction of metallocene 1 to pro 128.3, 127.1, 126.7, 126.4, 122.6, 21.5, 17.3, 14.0. duce (m-2-methyl-4-phenylindenyl)(m-pentameth ylcyclopentadienyl)Zirconium dichloride (1b) Example 1f 1664. In a 16 ml vial equipped with PTFE coated stir bar, Im-2-methyl-4-(4-tert-butylphenyl)indenyl(m-pen to a solution of 200 mg (0.40 mmol) of 1 in 10 ml of toluene, tamethylcyclopentadienyl)Zirconium dichloride (1f) 153 mg (0.45 mmol) of NaBPha and 4 mg (0.008 mmol) of 1675. Following the procedure described for 1c, 1.14 ml of Pd(PBus) were added. The reaction mixture was stirred for 0.80 M (0.91 mmol) 4-tert-butylphenylmagnesium bromide 12 hours at 90° C. The obtained suspension was filtered in ether, 2.00 ml of 0.5 M (1.00 mmol) ZnCl in THF,354 mg through Celite 503. Crystals that precipitated from the filtrate (0.70 mmol) of 1, and 0.70 ml of 0.02 M (0.014 mmol) at -30°C. were collected, washed with 5 ml of hexanes, and Pd(P'Bus), in THF gave yellowish solid. Yield 327 mg (84%). dried in vacuum. Yield 130 mg (65%) of yellowish solid. 1676 Anal. calc. for CHCl2r: C, 64.49; H, 6.49. 1665 Anal. calc. for CHCl2r: C, 62.13; H, 5.61. Found: C, 64.72; H, 6.62. Found: C, 62.29; H, 5.70. 1677 'H NMR (CDC1): 8 7.60 (m, 2H, 2,6-H in C.H.), 1666 'H NMR (CDC1): 8 7.62-7.69 (m, 2H, 2,6-H in 7.46 (m, 2H, 3.5-H in C.H.), 7.31 (dt, J=8.4 Hz, J=0.9 Hz, Ph), 7.28-7.47 (m, 4H, 7-Hin indenyland 3,4,5-H in Ph), 7.23 1H, 7-H in indenyl), 7.22 (dd, J–7.0 Hz, J=0.9 HZ, 1H, 5-H in (dd, J–7.0 Hz, J=0.9 HZ, 1H, 5-H in indenyl), 7.08 (dd, J–8.5 indenyl), 7.07 (dd, J=8.4 Hz, J=7.0 Hz, 1H, 6-H in indenyl), HZ, J=7.0 Hz, 1H, 6-H in indenyl), 6.70 (m, 1H, 1-H in 6.72 (m. 1H, 1-H in indenyl), 6.20 (d. J–2.2 Hz, 1H, 3-H in indenyl), 6.21 (d. J=2.3 Hz, 1H, 3-H in indenyl), 2.05 (s.3H, indenyl), 2.15 (s.3H, 2-Mein indenyl), 1.97 (s, 15H, CMes), 2-Mein indenyl), 1.88 (s, 15H, CMs). 1.33 (s, 9H, Bu). US 2010/01 13717 A1 May 6, 2010 66

1678 C{H} NMR (CDC1,): & 138.0, 137.9, 137.3, 1689 "C{H} NMR (CDC1,): & 135.8, 134.7, 133.1, 132.3, 131.2, 129.3, 128.8, 125.9, 125.6, 125.3, 121.3, 121.1, 132.9, 132.4, 132.1, 130.6, 130.09, 129.8, 126.83, 126.3, 114.7, 101.1, 34.9, 31.5, 16.1, 12.8. 122.7, 122.1, 118.4, 112.5, 101.9, 56.9, 17.3, 13.9. Example 1g Example 1k Im-2-methyl-4-(4-fluorophenyl)indenyl(m-pentam Im-2-methyl-4-(4-biphenyl)indenyl(m-pentameth ethylcyclopentadienyl)Zirconium dichloride (1g) ylcyclopentadienyl)Zirconium dichloride (1k) 1679. Following the procedure described for 1 c, 0.65 ml of 1690. Following the procedure described for 1c, 1.33 ml of 1.18 M (0.77 mmol) 4-fluorophenylmagnesium bromide in 0.31 M (0.41 mmol) 4-biphenylmagnesium bromide in THF, THF, 1.70 ml of 0.5 M (0.75 mmol) ZnC1 in THF, 300 mg 0.90 ml of 0.5 M (0.45 mmol) ZnCl, in THF, 350 mg (0.69 (0.59 mmol) of 1, and 0.59 ml of 0.02 M (0.012 mmol) mmol) of 1, and 0.69 ml of 0.02 M (0.014 mmol) Pd(PBus), Pd(P'Bus) in THF gave yellowish solid. Yield 271 mg (87%). in THF gave yellowish solid. Yield 61 mg (33%). 1680 Anal. calc. for C.H.ClFZr: C, 59.98; H, 5.23. 1691 Anal. calc. for CHC17r: C, 66.41; H, 5.57. Found: C, 60.03; H, 5.32. Found: C, 66.67; H, 5.60. 1681 H NMR (CDC1): 8 7.65 (m, 2H, 2,6-H in C.H.), 1692) H NMR (CDC1): 8 7.15-7.84 (m. 11H, CH, 7.35 (m. 1H, 5-H in indenyl), 7.02-7.23 (m, 4H, 6.7-H in CH and 5,7-Hin indenyl), 7.12 (dd, J=8.4 Hz, J=7.1 Hz, 1H, indenyl and 3.5-H in CH4), 6.65 (m. 1H, 1-H in indenyl), 6-H in indenyl), 6.79 (m. 1H, 1-H in indenyl), 6.23 (d. J–2.1 6.21 (d. J=2.2 Hz, 1H, 3-H in indenyl), 2.16 (s.3H, 2-Me in HZ, 1H, 3-H in indenyl), 2.19 (s.3H, 2-Me in indenyl), 2.01 indenyl), 1.99 (s. 15H, CMes). (s, 15H, CMes). 1682 'C{H} NMR (CDC1,): & 138.2, 133.6, 132.7, 1693) 'C{H} NMR (CDC1,): & 142.7, 142.3, 1418, 132.1, 132.0, 127.0, 126.8, 126.6, 123.0, 122.8, 122.5, 117.0, 140.5, 138.7, 133.4, 132.6, 130.8, 130.4, 130.3, 128.8, 128.7, 116.8, 102.4, 17.4, 14.0. 128.6, 126.8, 126.5, 122.7, 115.7, 102.4, 17.4, 14.0. Example 1h Example 11 m-2-methyl-4-(3-trifluoromethylphenyl)indenyl Im-2-methyl-4-(1-naphthyl)indenyl)(m-pentameth (m-pentamethylcyclopentadienyl)Zirconium dichlo ylcyclopentadienyl)Zirconium dichloride (11) ride (1h) 1694 Following the procedure described for lic, 2.23 ml of 0.15 M (0.33 mmol) 1-naphthylmagnesium bromide in THF, 1683. Following the procedure described for 1 c, 0.76 ml of 0.74 ml of 0.5 M (0.37 mmol) ZnCl, in THF, 130 mg (0.26 1.02 M (0.78 mmol) 3-trifluoromethylphenylmagnesium mmol) of 1, and 0.26 ml of 0.02 M (0.005 mmol) Pd(PBus), bromide in THF, 1.70 ml of 0.5M (0.85 mmol)ZnCl in THF, in THF gave yellowish solid. Yield 92 mg (65%). 300 mg (0.59 mmol) of 1, and 0.59 ml of 0.02 M (0.012 1695 Anal. calc. for CHC17r: C, 65.19; H, 5.47. mmol) Pd(PBus) in THF gave yellowish solid. Yield 245 mg Found: C, 65.53; H, 5.56. (72%). 1696 H NMR (CDC1): 8 7.10-7.97 (m, 7H, 5,6,7-H in 1684 Anal. calc. for CH,ClFZr: C, 56.83; H, 4.77. indenyl and naphthyl), 6.22 (dd, J-2.3 Hz, J-0.5 Hz, 1H, 3-H Found: C, 56.84; H, 4.88. in indenyl), 6.19 (m. 1H, 1-H in indenyl), 2.08 (s.3H, 2-Mein 1685 H NMR (CDC1): 87.92 (m, 2H, 2,6-H in C.H.), indenyl), 2.00 (s, 15H, CMes). 7.68 (m. 2H, 5,4-H in CH), 7.38 (m. 1H, 5-H in indenyl), 1697 C{H} NMR (CDC1): 8 139.6, 135.8, 133.1, 7.26 (m, 1H, 7-H in indenyl), 7.11 (dd, J=8.4 Hz, J–7.0 Hz, 133.0, 132.1, 130.52, 130.56 (two resonances), 130. 1, 129.8 6-H in indenyl), 6.64 (m. 1H, 1-H in indenyl), 6.23 (d. J–2.1 (two resonances), 126.8, 126.3, 122.7, 122.1, 116.4, 112.5, Hz, 3-H in indenyl), 2.17 (s, 3H, 2-Me in indenyl), 1.98 (s. 101.7, 17.2, 14.0. 15H, CMes). Example 1m Example li Im-2-methyl-4-(2-thienyl)indenyl(m-pentamethyl Im-2-methyl-4-(2-methoxyphenyl)indenyl(m-pen cyclopentadienyl)Zirconium dichloride (1m) tamethylcyclopentadienyl)Zirconium dichloride (1i) 1698. In a 16 ml vial equipped with a PTFE coated stir bar 1686. Following the procedure described for 1 c, 0.42 ml of to 2.16 ml of 0.30 M (0.64 mmol) of thiophene in THF, 1.29 0.86 M (0.36 mmol) 2-methoxyphenylmagnesium bromide ml of 0.5 M (1.29 mmol) "BuLi in hexanes was added by a in THF, 0.79 ml of 0.5 M (0.40 mmol) ZnCl in THF, 140 mg dosing pipette by vigorous stirring at -80° C. This mixture (0.69 mmol) of 1, and 0.28 ml of 0.02 M (0.013 mmol) was stirred and slowly warmed (for ca. 1 h) to 0°C. Then, 1.42 Pd(P'Bus) in THF gave yellowish solid. Yield 40 mg (27%). ml of 0.5 M (0.71 mmol)ZnCl in THF was added at -80°C., 1687 Anal. calc. for CHClOZr: C, 60.88; H, 5.68. and the obtained mixture was stirred and slowly warmed to Found: C, 61.01; H, 5.75. ambient temperature and then evaporated to dryness. In a 1688 H NMR (CDC1): 8 7.65 (dd, J=7.6 Hz, J=1.8 Hz, separate 16 ml vial equipped with a PTFE coated stir bar, to a 1H, 3-H in CH), 7.30-7.37 (m. 2H, 5,6-H in CH), 7.22 mixture of 250 mg (0.50 mmol) of 1,0.50 ml of 0.02 M(0.010 (dd, J–7.0 Hz, J=1.0 Hz, 1H, 5-H in indenyl), 7.07 (dd, J–8.4 mmol) Pd(PBus), in THF, and 4 ml of THF the above HZ, J=7.0 Hz, 1H, 6-H in indenyl), 7.02 (dt, J=7.6 Hz, J–1.1 described organozinc reagent were added. This mixture was HZ, 1H, 4-H in CH), 6.98 (dd, J=8.4 Hz, J=1.0 Hz, 1H, 7-H stirred for 4 hours at room temperature and then evaporated to in indenyl), 6.37 (m. 1H, 1-H in indenyl), 6.17 (dd, J-2.3 Hz, dryness. To the residue, a solution of 1.0 ml of MeSiCl, in 10 J=0.5 Hz, 1H, 3-H), 3.70 (s.3H, OMe), 2.14 (s.3H, 2-Me in ml of dry dichloromethane was added to eliminate an excess indenyl), 1.97 (s, 15H, CMes). of the organozinc reagent. The resulting mixture was stirred at US 2010/01 13717 A1 May 6, 2010 67 ambient temperature for 1 hour and then evaporated to dry 3-H in furyl, 6.19 (d. J=2.2 Hz, 1H, 3-H in indenyl), 2.07 (s, ness. In order to eliminate THF contamination, the residue 3H, 2-Mein indenyl), 1.94 (s, 15H, CMes). was treated with hot toluene (20 ml). The suspension was evaporated to dryness. The residue was additionally treated Example 1p with 60 ml of hot toluene, and the suspension formed was filtered through Celite 503. The toluene extract was evapo Im-2-methyl-4-(2-benzofuryl)indenyl(m-pentam rated to dryness. The obtained solid was washed with 3x15 ml of hexanes and dried in vacuum. Yield 192 mg (76%) of ethylcyclopentadienyl)Zirconium dichloride (1p) yellowish solid. 1699 Anal. calc. for CHC1-SZr: C, 56.67; H, 5.15. 1709. Following the procedure described for 1m, 3.10 ml Found: C, 56.95; H, 5.27. of 0.42M (1.30 mmol) of benzofuran, 2.62ml of 0.5M "BuLi 1700 "H NMR (CDC1): 8 7.43 (dd, J=3.6 Hz, J=1.1 Hz, (1.31 mmol), 2.89 ml of 0.5 M (1.45 mmol) ZnCl2 in THF, 1H, 5-H in thienyl), 7.30-7.36 (m, 3H, 5,7-H in indenyl and 510 mg (1.01 mmol) of 1, and 1.01 ml of 0.02 M (0.016 4-H in thienyl), 7.11 (dd, J=5.1 Hz, J=3.6 Hz, 1H, 3-H in mmol) Pd(PBus) in THF gave yellowish solid. Yield 374 mg thienyl), 7.03 (dd, J=8.5 Hz, J–7.0 Hz, 1H, 6-H in indenyl), (68%). 6.87 (im, 1H, 1-H in indenyl), 6.20 (d. J–2.2 Hz, 1H, 3-H in 1710 Anal. calc. for CHClOZr: C, 61.97; H, 5.20. indenyl), 2.18 (s.3H, 2-Mein indenyl), 1.96 (s, 15H, CMes). Found: C, 62.05; H, 5.22. 1701] 'C{H} NMR (CDC1,): & 143.8, 133.0, 132.5, 1711 H NMR (CD): 8 7.91 (dd, J–7.2 Hz, J=0.8 Hz, 132.4, 129.3, 129.0, 127.5, 126.8, 126.6, 126.5, 126.3, 122.9, 1H, 5-H in indenyl), 7.32-7.41 (m,3H,3,4,7-H in benzothie 115.4, 102.7, 17.5, 13.9. nyl), 7.18 (m, 1H, 1-H in indenyl), 7.03-7.08 (m, 3H, 7-H in indenyl and 5,6-H in benzothienyl), 6.92 (dd, J=8.6 Hz, J-7.2 Example lin HZ, 1H, 6-H in indenyl), 5.70 (d. J=2.2 Hz, 1H, 3-H in inde Im-2-methyl-4-(2-benzothienyl)indenyl(m-pentam nyl), 2.05 (s.3H, 2-Mein indenyl), 1.77 (s, 15H, CMes). ethylcyclopentadienyl)Zirconium dichloride (1n) Example 1 q 1702 Following the procedure described for 1 m, 2.02 ml of 0.52 M (1.05 mmol) of benzothiophene, 2.11 ml of 0.5 M Heck reaction of metallocene 1 to produce cis- and "BuLi (1.06 mmol), 2.32 ml of 0.5 M (1.16 mmol) ZnCl in trans-isomers of (2-methyl-4-styrylindenyl)(pentam THF, 410 mg (0.81 mmol) of 1, and 0.81 ml of 0.02 M (0.016 ethylcyclopentadienyl)Zirconium dichloride (1q) mmol) Pd(PBus) in THF gave yellowish solid. Yield 143 mg (31%). 1712 1703. Anal. calc. for CHC1-SZr: C, 60.19; H, 5.05. Found: C, 60.34; H, 5.20. 1704 H NMR (CDC1): 8 7.76-7.85 (m, 2H, 4.7-H in benzothienyl), 7.66 (s, 1H, 3-H in benzothienyl), 7.26-7.48 (m, 4H, 5.7-Hin indenyland 5,6-H in benzothienyl), 7.08 (dd. styrene J=8.5 Hz, J=7.1 Hz, 1H, 6-H in indenyl), 6.98 (m, 1H, 1-H in LiN(SiMe3) indenyl), 6.23 (d. J=2.1 Hz, 1H, 3-H in indenyl), 2.21 (s.3H, G Pd(PBus) 2-Mein indenyl), 1.98 (s, 15H, CMes). ZrCl 1705 C{H} NMR (CDC1,): & 142.1, 141.1, 133.4, 132.6, 132.4,128.9, 127.4, 126.8, 126.0, 125.9, 126.7, 126.4, 61 125.9, 125.4, 124.1, 123.7, 123.61, 123.58, 115.4, 102.7, 17.5, 14.0. Example lo Im-2-methyl-4-(2-furyl)indenyl(m-pentamethylcy clopentadienyl)Zirconium dichloride (1o) 1706 Following the procedure described for 1 m, 1.19 ml of 0.37M (0.44 mmol) of furan, 0.88 ml of 0.5M "BuLi (0.44 mmol), 0.96 ml of 0.5 M (0.48 mmol) ZnCl2 in THF, 170 mg (0.34 mmol) of 1, and 0.34 ml of 0.02 M (0.007 mmol) Pd(PBus) in THF gave yellowish solid. Yield 80 mg (48%). 1707 Anal. calc. for CHClOZr: C, 58.52; H, 5.32. Found: C, 58.66; H, 5.37. ZrCl 1708 H NMR (CDC1): 8 7.51-7.55 (m, 2H, 5-H in indenyl and 5-H in furyl), 7.32 (dt, J=8.5 Hz, J=0.9 HZ, 1H, 7-H in indenyl), 7.06 (dd, J=8.5 Hz, J–7.2 Hz, 1H, 6-H in indenyl), 6.94 (m. 1H, 1-H in indenyl), 6.81 (dd, J-3.4 Hz, J=0.7 Hz, 1H, 4-H in furyl), 6.52 (dd, J=3.4 Hz, J=1.8 Hz, 1H, US 2010/01 13717 A1 May 6, 2010

-continued -continued O

OG ZrCl 61

1713 To a solution of 200 mg (0.40 mmol) of 1 in 5 ml of O'Bu toluene, 45.5 mg (0.45 mmol) of freshly distilled styrene, 199 mg (1.19 mmol) of LiN(SiMe), and 0.40 ml of 0.02 M (0.0079 mmol.2%) of Pd(PBus), intoluene were added. This 1717. In a 16 ml vial equipped with PTFE coated stir bar, mixture was stirred for 20 hours at ambient temperature; then, to a solution of 200 mg (0.40 mmol) of 1 in 10 ml of toluene, for 20 hours at 90°C. The resulting mixture was evaporated to 58 mg (0.48 mmol) of 4-fluorostyrene, 199 mg (1.19 mmol) dryness. To the residue, a solution of 1.0 ml of MeSiCl, in 10 of LiN(SiMe), and 0.40ml (0.008 mmol) of 0.02 Msolution ml of methylene chloride was added. This mixture was stirred of Pd(PBus) in toluene were added. The reaction mixture for 1 hour at room temperature, then, evaporated to dryness. was stirred for 20 hat room temperature and then for 24h at To the residue, 20 ml of toluene was added. The resulting 90°C. The reaction mixture was cooled to ambient tempera mixture was filtered through a glass frit (G4). The filtrate was ture, and 172 mg (1.58 mmol) of MeSiC1 was added. The evaporated to dryness. The crude product was washed with resulting mixture was stirred for 10hat room temperature and 3x15 ml of hexanes and dried in vacuum. Yield, 170 mg then evaporated to dryness. The residue was washed with 4x8 (81%) of yellowish solid. The product is a mixture of trans ml of hexanes on a glass frit (G4). The combined filtrate was and cis-isomers, ca. 3 to 1 based on the NMR spectra. evaporated to dryness, and the residue was dried in vacuum. 1714 Anal. calc. for CHCl2r: C, 63.61; H, 5.72. Yield 66 mg (30%) of yellow solid of pure trans-isomer. Found: C, 63.88; H, 5.80. 1718. Anal. calc. for CHC1FZr: C, 61.52; H, 5.35. 1715) 'H NMR (CDC1): 8 7.56-7.61 (m, 2H, 2,6-H in Found: C, 61.75; H, 5.48. Ph), 7.21-7.45 (m, 6H,3,4,5-H in Phand 5,6,7-H in indenyl), 1719 HNMR (CDC1): 87.56(m,2H,3,5-Hin CHF), 7.03-7.12 (m, 2H, CH=CH), 6.81 and 6.84 (two m, 1H, 3-H 7.41 (m. 1H, 5-H in indenyl), 7.36 (m. 1H, 7-H in indenyl), in indenyl), 6.19 and 6.22 (two m, 1H, 1-H in indenyl), 7.26 (m. 2H, 2,6-H in CHF), 7.10 (m. 1H, 6-H in indenyl), 2.20-2.25 (m, 3H, 2-Me in indenyl), 1.99-2.07 (m. 15H, 7.04-7.08 (m, 2H, CH=CH), 6.83 (m. 1H, 1-H in indenyl), CMes). 6.19 (d. J–2.1 Hz, 3-H in indenyl), 2.25 (s, 3H, 2-Me in indenyl), 1.99 (s. 15H, CMes). Example 1r Example 1s Heck reaction of metallocene 1 to produce trans-(2- methyl-4-(4-fluorostyryl)indenyl)(pentamethylcyclo Heck reaction of metallocene 1 to produce cis- and pentadienyl)Zirconium dichloride (1q) trans-isomers of (2-methyl-4-(12-n-butoxyvinyl) indenyl)(pentamethylcyclopentadienyl)Zirconium 1716 dichloride (1s) 1720

CHFCHO'Bu, LiN(TMS) CH=CHO'Bu, LiN(TMS) Pd(PBu3)2, toluene, Cl2Zr Pd(PBus), toluene, rt...90° C. rt ...90° C. Her Clzr s He Br US 2010/01 13717 A1 May 6, 2010 69

-continued -continued

O'Bu

1721. In 16 ml vial equipped with PTFE coated stir bar, to 2a-2d a solution of 200 mg (0.40 mmol) of 1 in 10 ml of toluene, 48 R = Me (2a), 4-MeC6H4 (2b), 3-MeCH4 (2c), 4-EuCH4 (2d). mg (0.48 mmol) of n-butyl vinyl ether, 199 mg (1.19 mmol) of LiN(SiMe), and 0.40ml (0.008 mmol) of 0.02M solution of Pd(PBus) in toluene were added. The reaction mixture was stirred for 20 hat room temperature and then 20 hat 90° Example 2a C. The reaction mixture was cooled to ambient temperature, Negishi reaction of metallocene 2 to produce (m-2, and 172 mg (1.58 mmol) of MeSiCl was added. The result 4-dimethylindenyl)(m-pentamethylcyclopentadi ing mixture was stirred for 10 hat room temperature and then enyl)hafnium dichloride (2a) evaporated to dryness. The residue was washed with 50 ml of hexanes on glass frit (G4). The filtrate was evaporated to 1725. Following the procedure described for 1a, 600 mg dryness, and the residue was dried in vacuum. Yield 82 mg (1.01 mmol) of 2, 0.66 ml of 2.0 M MeZnC1 (1.32 mmol) in (39%) of yellowish solid of a ca. 1:2 mixture of cis- and THF, and 1.01 ml of 0.02 M(0.020 mmol) Pd(P'Bus), in THF trans-isomers. gave yellowish solid. Yield 482 mg (90%). 1726. Anal. calc. for CHCl2.Hf: C, 47.79; H, 4.96. 1722 Anal. calc. for CHClOZr: C, 59.52; H, 6.53. Found: C, 47.87; H, 5.02. Found: C, 59.82; H, 6.69. 1727 H NMR (CD): 8 7.02 (m. 1H, 5-H in indenyl), 1723 "H NMR (CDC1): 8 727-7.57 (m, 1H, 6.88 (m. 1H, 7-H in indenyl), 6.80 (dd, J=8.2 Hz, J=6.8 Hz, CH=CHOCH), 6.91-7.24 (m, 3H, 5,6,7-H in indenyl), 1H, 6-H in indenyl), 6.45 (m. 1H, 1-H in indenyl), 5.56 (d. 6.56-6.63 (m. 1H, 1-H in indenyl), 6.08-6.12 (m, 1H, 3-H in J=2.2 Hz, 1H, 3-H in indenyl), 2.42 (s.3H, 4-Mein indenyl), indenyl), 6.01 and 6.43 (two m, 1H, CH=CHOCH), 3.85 2.11 (s3H, 2-Me in indenyl), 1.85 (s, 15H, CMs). 4.04 (m, 2H, OCHCHCHMe), 2.20 and 2.21 (two s, 3H, 1728 C{H} NMR (CD): & 135.3, 1344, 130.9, 126. 2-Me in indenyl), 1.97 and 1.96 (two s, 15H, CMes), 1.71 3,125.1, 122.5, 119.5, 119.3, 109.5, 99.0, 20.1, 16.7, 12.5. (m. 2H, OCHCHCHMe), 1.46 (m. 2H, OCHCHCHMe), 0.97 (m, 3H, OCHCHCHMe). Example 2b (m-2-methyl-4-p-tolylindenyl)(m-pentamethylcy Examples 2a-2d clopentadienyl)hafnium dichloride (2b) Negishi coupling applying (m-2-methyl-4-bromoin 1729. Following the procedure described for 1 c, 0.66 ml of denyl)(m-pentamethylcyclopentadienyl)hafnium 1.0 M (0.66 mmol) p-tolylmagnesium bromide in THF, 1.45 dichloride (2) ml of 0.5 M (0.73 mmol) ZnCl2 in THF, 300 mg (0.51 mmol) of2, and 0.51 ml of 0.02 M (0.010 mmol) Pd(PBus), in THF 1724 gave yellowish solid. Yield 219 mg (72%). 1730. Anal. calc. for CHC17r: C, 53.70; H, 5.01. Found: C, 53.96: H, 5.13. Br 1731. HNMR (CDC1): 87.53 (m,2H, 2,6-Hinp-tolyl), 7.31 (dt, J–8.5 Hz, J=0.8 Hz, 1H, 7-H in indenyl), 7.23 (m, 2H,3,5-H in p-tolyl), 7.18 (dd, J=6.9 Hz, J=0.8 Hz, 1H, 5-H in indenyl), 7.03 (ddd, J=8.5 Hz, J=6.9 Hz, J–0.6 Hz, 1H, 6-H in indenyl), 6.60 (m. 1H, 1-H in indenyl), 6.15 (d. J=2.2 Hz, C RZnCl 1H,3-H in indenyl), 2.36 (s.3H, 4-Me in p-tolyl), 2.20 (s.3H, 2-Me in indenyl), 2.03 (s, 15H, CMes). HISC Pd(PPts):-THF Example 2c (m-2-methyl-4-m-tolylindenyl)(m-pentamethylcy clopentadienyl)hafnium dichloride (2c) 1732 Following the procedure described for 1c, 1.10 ml of 1.0 M (1.10 mmol) m-tolylmagnesium chloride in THF, 2.41 ml of 0.5 M (1.21 mmol) ZnCl2 in THF, 500 mg (0.84 mmol)

US 2010/01 13717 A1 May 6, 2010 77

3,3'-H of furyl), 6.06 (m, 2H, 4,4'-H of furyl), 2.33 (m, 6H, Example rac-8n 5,5'-Me of furyl), 2.23 (s, 6H, 2,2'-Me of indenyl), 1.29 (s, 6H, SiMe...). rac-Dimethylsilyl-bism-2-methyl-4-(1-naphthyl) inden-1-ylzirconium dichloride (rac-8n) Example rac-81 1843. In 16 ml vial equipped with PTFE coated stir bar and rac-Dimethylsilyl-bism-2-methyl-4-(2-benzothie containing 8.80 ml of 0.25 M(2.20 mmol)ZnC1 in THF, 2.00 nyl)inden-1-ylzirconium dichloride (rac-81) ml of 1.0 M (2.00 mmol) 1-naphthylmagnesium bromide in THF was added at room temperature. This mixture was stirred 1836. In a 16 ml vial equipped with a PTFE coated stir bar, for 1 hour. Then, in a separate 16 ml vial equipped with PTFE to 1.57 ml of 0.30 M (0.82 mmol) of thiophene in THF, 1.64 coated Stir bar containing a Suspension of 200 mg (0.32 ml of 0.5 M (0.82 mmol) "BuLi in hexanes was added by a mmol) of rac-8 in 2.0 ml of THF, 4.42 ml of the solution of the dosing pipette by vigorous stirring at -80° C. This mixture above obtained organozinc reagent and 0.65 ml of 0.02 M was stirred and slowly warmed (for ca. 1 h) to 0°C. Then, 1.80 (0.013 mmol) Pd(P'Bus) in THF were added by a dosing ml of 0.5 M(0.90 mmol)ZnCl in THF was added at -80°C., pipette. The reaction mixture was stirred for 2 hours at 70° C. and the obtained mixture was stirred and slowly warmed to and then evaporated to dryness. To the residue, 10 ml of dry ambient temperature and then evaporated to dryness. In a dichloromethane and 1.0 ml of MeSiCls were added. This separate 16 ml vial equipped with PTFE coated stir bar, to a mixture was stirred for 1 hour and then evaporated to dryness. mixture of 200 mg (0.32 mmol) of rac-8, 0.63 ml of 0.02 M To the residue, 20 ml of toluene was added. This mixture was (0.013 mmol) Pd(PBus), in THF, and 4 ml of THF the above refluxed for 10 min, cooled and evaporated to dryness. Then, described organozinc reagent was added. This mixture was 60 ml of toluene was added, and the resulted suspension was stirred for 2 hours at 70° C. and thenevaporated to dryness. To filtered through glass frit (G4). The filtrate was evaporated to the residue, 5 ml of dry dichloromethane was added, then, this dryness. The residue was washed by 3x15 ml of hexanes and mixture was filtered through a glass frit (G4). The precipitate dried in vacuum. Yield 106 mg (46%) of yellow-orange solid. was washed with 3x5 ml of THF, 3x5 ml of CHCl, 10 ml of 1844 Anal. calc. for CHClSizr: C, 69.20; H, 4.70. hexanes and then dried in vacuum. Yield 180 mg (77%) of Found: C, 68.99; H, 4.82. yellow solid. 1845 H NMR (CDC1): 8 7.87 (im, 4H, 5,5,8,8-H in 1837 Anal. calc. for C.H.C1-S-SiZr: C, 61.59; H, 4.08. naphthyl), 7.74 (m, 2H, 3,3'-H in naphthyl), 7.71 (m, 2H, Found: C, 61.83; H, 3.82. 4,4'-H in naphthyl), 7.53 (dd, J=8.2 Hz, J–7.0 Hz, 2H, 7.7"-H 1838 H NMR (CDC1): 8 7.77 (m, 4H, 4,4',7,7-H of of indenyl), 7.48 (m. 2H, 5,5'-H of indenyl), 7.42 (m. 2H, benzothienyl), 7.71 (d. J=8.7 Hz, 2H, 7.7"-Hof indenyl), 7.60 6,6'-H in naphthyl), 7.28 (m, 2H, 7.7"-H in naphthyl), 7.12 (s. 2H, 3,3'-H of benzothienyl), 7.57 (d. J=7.1 Hz, 2H, 5,5'-H (dd, J=8.7 Hz, J–7.0 Hz, 2H, 6,6'-H of indenyl), 6.38 (s. 2H, of indenyl), 7.29 (m, 4H, 5.5',6,6'-Hofbenzothienyl), 7.21 (s, 3,3'-H of indenyl), 2.17 (s, 6H, 2,2'-Me in indenyl), 1.34 (s. 2H, 3,3'-H of indenyl), 7.11 (dd, J=8.7 Hz, J=7.1 Hz, 2H, 6H, MeSi). 6,6'-H of indenyl), 2.26 (s, 6H, 2,2'-Me of indenyl), 1.34 (s. 6H, SiMe...). Examples meso-8b 1839 C{H} NMR (CDC1,): & 144.7, 138.3, 138.1, 137.6, 135.6, 133.3, 130.2, 130. 1, 128.3, 128.1 (two reso Negishi coupling applying meso-dimethylsilyl-bis nances), 127.4 (three resonances), 121.8, 120.6, 72.4, 20.7. (m-4-bromo-2-methylinden-1-yl)zirconium dichlo ride (meso-8); synthesis of meso-dimethylsilyl-bis 0.7. (m-2-methyl-4-p-tolylinden-1-yl)zirconium Example rac-8m dichloride (meso-8b) rac-Dimethylsilyl-bism-2-methyl-4-(2-benzofuryl) 1846 inden-1-ylzirconium dichloride (rac-8m) Br 1840. Following the procedure described for rac-81, 1.64 ml of 0.50 M (0.82 mmol) of benzofuran in THF, 1.64 ml of 0.5 M "BuLi (0.82 mmol) in hexanes, 1.80 ml of 0.5 M(0.90 mmol) ZnCl2 in THF, 200 mg (0.32 mmol) of 8, and 0.63 ml of 0.02 M (0.013 mmol) Pd(PBus), in THF gave an orange RZnCl solid. Yield 66 mg (30%). 1C (Pd(PBu3)2 1841 Anal. calc. for CHClOSiZr: C, 64.39; H, 4.27. MeSi ZrS THF Found: C, 64.16; H, 4.29. C 1842 'H NMR (CDC1): 8 7.80 (m, 2H, 5.5/6,6'-H of benzofuryl), 7.74 (m,2H, 6,6/5,5'-Hofbenzofuryl), 7.71 (m, 2H, 7.7"-H of indenyl), 7.60 (s. 2H, 3,3'-H of benzofuryl), 7.57 (dd, J=7.1 Hz, J=0.6 Hz, 2H, 5,5'-Hof indenyl), 7.29 (m, 4H, 4,4,7,7-Hofbenzofuryl), 7.21 (s.2H,3,3'-Hof indenyl), Br 7.11 (dd, J–8.7 Hz, J=7.1 Hz, 2H, 6,6'-Hof indenyl), 2.26 (s, meso-8 6H, 2,2'-Me of indenyl), 1.34 (s, 6H, SiMe...).

US 2010/01 13717 A1 May 6, 2010 79

Example rac-9c Examples 10a–10o rac-Dimethylsilyl-bis(m-3-p-tolyl-5-methylcyclo Negishi coupling using 4,4'-sulfandiyl-bis(m-7- pentabthien-6-yl)Zirconium dichloride (rac-9c) bromo-2-methylindenyl)Zirconium dichloride (10) 1859. Following the procedure described for 1 c, 0.80ml of 1871 1.0 M (0.80 mmol) phenylmagnesium bromide in THF, 1.77 ml of 0.5 M (0.89 mmol) ZnCl in THF, 200 mg (0.31 mmol) of rac-9, and 0.62 ml of 0.02 M (0.012 mmol) Pd(PBus), in Br R THF gave yellow solid for 2 hours at 70° C. Yield 197 mg (95%). 1860 Anal. calc. for CHCl2SSi Zr: C, 57.46; H, 4.52. Found: C, 57.70; H, 4.66. C RZnCl C 1861 "H NMR (CDC1): 8 7.41-7.52 (m, 6H, 5,5'-H of 1'-' Pd(PBus) 1. cyclopentathienyl and 2.2".6,6'-H of p-tolyl), 7.16-7.24 (m, S ZrN ---THF S Zr No 4H, 3,3',5,5'-H of p-tolyl), 6.83 (s. 2H, 3,3'-H of cyclopen tathienyl), 2.32 (s, 6H, 4,4'-Me of p-tolyl), 2.31 (s, 6H, 2,2'- Me of cyclopentathienyl), 1.08 (s, 6H, SiMe3). 1862 'C{H} NMR (CDC1,): & 145.8, 144.8, 139.4, 138.2, 133.4, 131.1, 130.0, 128.4, 121.5, 120.5, 72.4, 22.5, 20.7, 0.8. Br R R = Me (10a), Ph (10b) 4-MeC6H4 (10c), 3-MeC6H4 (10d),4-BuCH4 (10e), 2.4.6- MeCH (10f), 5-methyl-2-thienyl (10g), 5-methyl-2-furyl (10h), 2-benzothienyl Example rac-9d (10i), 2-benzofuryl (10k), 4-FCH (101), 3-CFCH (10m), 2,5-dimethylphenyl rac-Dimethylsilyl-bis(m-3-m-tolyl-5-dimethylcyclo (10n), 4-biphenyl (10o). pentabthien-6-yl)Zirconium dichloride (rac-9d) 1863. Following the procedure described for 1 c, 0.76 ml of Example 10a 1.0 M (0.76 mmol) m-tolylmagnesium chloride in THF, 1.68 4,4'-Sulfandiyl-bis(m-2,7-dimethylindenyl)zirco ml of 0.5M (0.84 mmol) ZnCl, in THF, 190 mg (0.29 mmol) of rac-9, and 0.59 ml of 0.02 M (0.012 mmol) Pd(P'Bus) in nium dichloride (10a) THF gave yellow solid for 2 hours at 70° C. Yield 124 mg 1872 Under a nitrogen atmosphere, in a 16 ml vial (63%). equipped with PTFE coated stir bar and a suspension of 286 1864 Anal. calc. for CHCl2SSi Zr: C, 57.46; H, 4.52. mg (0.47 mmol) of 10 in 8.0 ml of THF, 0.61 ml of 2.0 M Found: C, 57.61; H, 4.59. MeZnC1 (1.22 mmol) in THF and 0.94 ml of 0.02 M (0.019 1865 H NMR (CDC1): 8 7.47 (s. 2H, 5,5'-H of cyclo mmol) Pd(PBus) in THF were added by a dosing pipette. pentathienyl), 7.06-7.44 (m, 8H, 2,2'44".5.5'6,6'-H of The reaction mixture was stirred for 2 hours at 70° C. and then m-tolyl), 6.85 (m. 2H, 3,3'-H of cyclopentathienyl), 2.34 (s. evaporated to dryness. To the residue, a solution of 1.0 ml of 6H, 3,3'-Me of m-tolyl), 2.32 (s, 6H, 2,2'-Me of cyclopen MeSiCls in 10 ml of dry dichloromethane was added to elimi tathienyl), 1.09 (s, 6H, SiMe). nate an excess of the organozinc reagent. The resulting mix 1866 'C{H} NMR (CDC1,): & 144.7, 140.1, 1376, ture was stirred at ambient temperature for 1 hour and then 136.1, 135.9, 130.6, 130.3, 130. 1, 129.1, 125.6, 121.5, 120.4, evaporated to dryness. In order to eliminate THF contamina 72.5, 22.8, 20.7, 0.7. tion, toluene (20 ml) was added and the mixture was vigor ously stirred and brought to reflux; then the Suspension was Example rac-9e evaporated to dryness. This procedure was repeated a second time using 60 ml of toluene, and the resulting Suspension was rac-dimethylsilyl-bism-3-(4-tert-butylphenyl)-5- filtered through Celite 503. The resulting toluene filtrate was dimethylcyclopentab thien-6-ylzirconium dichlo evaporated to dryness. The obtained solid was washed with ride (rac-9e) 3x15 ml of hexanes and dried in vacuum. Yield, 210 mg (93%) of a yellow solid. 1867 Following the procedure described for 1c, 1.00 ml of 1873 Anal. calc. for CHC1-SZr: C, 55.21; H, 4.21. 0.80 M (0.80 mmol) 4-tert-butylphenylmagnesium bromide Found: C, 55.35; H, 4.16. in ether, 1.75 ml of 0.5 M (0.88 mmol) ZnCl, in THF, 198 mg 1874 H NMR (300 MHz, CDC1): 8 7.51 (d. J=7.1 Hz, (0.31 mmol) of rac-9, and 0.61 ml of 0.02 M (0.012 mmol) 2H, 5,5'-H), 6.95 (m, 2H, 6,6'-H), 6.39 (d. J=2.3 Hz, 2H, Pd(P'Bus) in THF gave yellow solid for 2 hours at 70° C. 1,1'-H), 4.52 (d. J=2.3 Hz, 2H,3,3'-H), 2.52 (s, 6H, 7.7-Me), Yield 185 mg (79%). 2.06 (s, 6H, 2,2'-Me). 1868 Anal. calc. for CHCl2SSi Zr: C, 60.60; H, 5.62. 1875 'C{H} NMR (75 MHz, CDC1): 8 143.6, 143.2, Found: C, 60.86; H, 5.75. 132.8, 130.3, 127.0, 125.3, 110.9, 106.4, 105.1, 21.3, 18.6. 1869 H NMR (CDC1): 8 737-7.61 (m, 10H, 5,5'-H of cyclopentathienyl and 2.2.3,3'5.5".6,6'-H of CH), 6.85 (s. Example 10b 2H, 3,3'-H of cyclopentathienyl), 2.31 (s, 6H, 2,2'-Me of cyclopentathienyl), 1.29 (s. 18H, Bu), 1.09 (s, 6H, SiMe). 4,4'-Sulfandiyl-bis(m-7-phenyl-2-methylindenyl) 1870 °C{H} NMR (CDC1,): & 138.3, 138.1, 137.6, zirconium dichloride (10b) 135.6, 133.3, 130.1, 128.1, 127.4, 121.5, 120.6, 72.5, 36.1, 1876 Under a nitrogen atmosphere, in a 16 ml vial 32.6, 20.7, 0.7. equipped with a PTFE coated stir bar, 0.57 ml of 1.0 M (0.57 US 2010/01 13717 A1 May 6, 2010 mmol) phenylmagnesium bromide in THF was added by a 1885 H NMR (300 MHz, CDC1): 8 7.73 (d. J–7.3 Hz, dosing pipette to a mixture of 1.25 ml of 0.5 M (0.63 mmol) 2H, 5,5'-H), 7.16-7.52 (m, 10H, 6,6'-H in indenyl and 2,2',4, ZnCl2 in THF and 5 ml of THF with vigorous stirring at 4'5.5", 6,6'-H in m-tolyl), 6.60 (d. J=2.2 Hz, 2H, 1,1'-H), 4.79 ambient temperature. This organozinc reagent was addition (d. J=2.2 Hz, 2H,3,3'-H), 2.39 (s, 6H, 4,4'-Mein p-tolyl), 2.09 ally stirred for 1 hour and then added to a mixture of 133 mg (s, 6H, 2,2'-Me). (0.22 mmol) of 10, 0.44 ml of 0.02 M (0.009 mmol) Pd(P'Bus) in THF, and 2 ml of THF placed in a separate 16 1886 C{H} NMR (75 MHz, CDC1): 8 143.5, 138.7, ml vial equipped with a PTFE coated stir bar. The reaction 138.6, 136.2, 135.9, 131.3, 130.3, 130.0 (two resonances), mixture was stirred for 2 hours at 70° C. and then evaporated 127.8, 127.2, 124.6, 110.7, 106.1, 103.3, 22.8, 18.5. to dryness. To the residue, a solution of 1.0 ml of MeSiCls in 10 ml of dry dichloromethane was added to eliminate an Example 10e excess of the organozinc reagent. The resulting mixture was stirred at ambient temperature for 1 hour and then evaporated 4,4'-Sulfandiyl-bism-2-methyl-7-(4-tert-butylphe to dryness. In order to eliminate THF contamination, toluene nyl)indenylzirconium dichloride (10e) (20 ml) was added and the mixture was vigorously stirred and brought to reflux; then the Suspension was evaporated to 1887 Under a nitrogen atmosphere, in a 16 ml vial dryness. This procedure was repeated a second time using 60 equipped with PTFE coated stir bar, 0.98 ml of 0.8 M (0.78 ml of toluene, and the resulting Suspension was filtered mmol) 4-tert-butylphenylmagnesium bromide in ether was through Celite 503. The resulting toluene filtrate was evapo added by a dosing pipette to a mixture of 0.87 ml of 0.5 M rated to dryness. The obtained solid was washed with 3x15 ml (0.44 mmol) ZnCl2 in THF and 5 ml of THF with vigorous of hexanes and dried in vacuum. Yield, 50 mg (38%) of a stirring at ambient temperature. This organozinc reagent was yellow solid. additionally stirred for 1 hour and then added to a mixture of 1877 Anal. calc. for CHC1-SZr: C, 63.77; H, 4.01. 184 mg (0.30 mmol) of 10, 0.61 ml of 0.02 M (0.012 mmol) Found: C, 63.94; H, 3.92. Pd(P'Bus), in THF, and 2 ml of THF placed in a separate 16 1878 H NMR (300 MHz, CDC1): 8 7.74 (d. J=7.2 Hz, ml vial equipped with PTFE coated stir bar. The reaction 2H, 5,5'-H), 7.62-7.69 (m, 4H, 2,2',6,6'-H in Ph), 7.33-7.49 mixture was stirred for 2 hours at 70° C. and then evaporated (m, 6H, 3,3'44",5,5'-H in Ph), 7.23 (d. J=7.2 Hz, 2H, 6,6'-H), to dryness. The product was extracted with 3x30 ml of hex 6.59 (d. J–2.2 Hz, 2H, 1,1'-H), 4.80 (d. J=2.2 Hz, 2H,3,3'-H), anes. The yellow solution was evaporated to dryness, and the 2.08 (s, 6H, 2,2'-Me). residue was washed with 10 ml of cold hexanes and dried in Example 10c vacuum. Yield, 176 mg (81%) of a yellow solid. 1888 Anal. calc. for CHCISZr: C, 67.20; H, 5.64. 4,4'-Sulfandiyl-bis(m-2-methyl-7-p-tolyl-indenyl) Found: C, 67.48; H, 5.74. Zirconium dichloride (10c) 1889 'H NMR (300 MHz, CDC1): 8 7.72 (d. J–7.3 Hz, 1879 Under a nitrogen atmosphere, following the proce 2H, 5,5'-H), 7.59-7.67 (m, 4H, 2,2',6,6'-H in CH), 7.40-7.48 dure described for 10b, 0.79 ml of 1.0M (0.79 mmol)p-tolyl (m, 4H, 3,3',5,5'-H in CH), 7.23 (d. J–7.3 Hz, 2H, 6,6'-H), magnesium bromide in THF, 1.74 ml of 0.5 M (0.87 mmol) 6.62 (d. J–2.3 Hz, 2H, 1,1'-H), 4.80 (d. J=2.3 Hz, 2H,3,3'-H), ZnCl2 in THF, 185 mg (0.30 mmol) of 10, and 0.61 ml of 0.02 2.08 (s, 6H, 2,2'-Me), 1.33 (s, 18H, Bu). M (0.012 mmol) Pd(P'Bus), in THF gave a yellow solid for 2 1890 °C{H} NMR (75 MHz, CDC1): 8 143.5, 139.3, hours at 70° C. Yield, 104 mg (54%). 138.6, 137.9, 135.6, 130.3, 130.0, 128.1, 127.0, 118.2, 110.7, 1880 Anal. calc. for CHCl2SZr: C, 64.74; H, 4.47. 106.2, 104.6, 36.2, 32.7, 18.5. Found: C, 64.89; H, 4.40. 1881 H NMR (300 MHz, CDC1): 8 7.72 (d. J=7.4 Hz, 2H, 5,5'-H), 7.52-7.58 (m, 4H, 2,2',6,6'-H in p-tolyl), 7.23-7. Example 10f 29 (m, 4H, 3,3',5,5'-H in p-tolyl), 7.21 (d. J=7.4 Hz, 2H, 6,6'-H), 6.59 (d. J=2.5 Hz, 2H, 1,1'-H), 4.77 (d. J=2.5 Hz, 2H, 4,4'-Sulfandiyl-bis(m-7-mesityl-2-methylindenyl) 3,3'-H), 2.37 (s, 6H, 4,4'-Mein p-tolyl), 2.07 (s, 6H, 2,2'-Me). zirconium dichloride (101) 1882 'C{H} NMR (75 MHz, CDC1): 8 143.4, 139.6, 139.3, 137.9, 135.6, 130.7, 130.5, 130.0, 127.0, 122.9, 110.5, 1891 Under a nitrogen atmosphere, following the proce 106.1, 103.3, 22.5, 18.5. dure described for 10b, 0.97 ml of 0.88 M (0.85 mmol) mesitylmagnesium bromide in THF, 1.88 ml of 0.5 M (0.94 Example 10d mmol) ZnCl2 in THF, 200 mg (0.33 mmol) of 10, and 0.66 ml of 0.02M (0.013 mmol) Pd(P'Bus) in THF gave yellow solid 4,4'-Sulfandiyl-bis(m-2-methyl-7-m-tolylindenyl) for 2 hours at 70° C. Yield, 214 mg (95%). Zirconium dichloride (10d) 1892 Anal. calc. for CHC1-SZr: C, 66.45; H, 5.28. 1883 Under a nitrogen atmosphere, following the proce Found: C, 66.11; H, 5.39. dure described for 10b, 0.53 ml of 1.0M (0.53 mmol) m-tolyl 1893 H NMR (300 MHz, CDC1): 8 7.71 (d. J–7.3 Hz, magnesium chloride in THF, 1.16 ml of 0.5 M (0.58 mmol) 2H, 5,5'-H of indenyl), 7.06 (d. J–7.3 Hz, 2H, 6,6'-H of ZnC1 in THF, 123 mg (0.20 mmol) of 10, and 0.40 ml of 0.02 indenyl), 6.96 (m, 2H, 3,3'-Hofmesity1), 6.91 (m,2H, 3,3'-H M (0.008 mmol) Pd(PBus) in THF gave yellow solid for 2 of mesity1), 6.04 (m. 2H, 1,1'-H of indenyl), 4.87 (n, 2H, hours at 70° C. Yield, 85 mg (67%). 3,3'-H of indenyl), 2.29 (s. 6H, 2,2'-Me of mesity1), 2.19 (s. 1884 Anal. calc. for CHCl2SZr: C, 64.74; H, 4.47. 6H, 4,4'-Me of mesity1), 2.08 (s, 6H, 6,6'-Me of mesity1), 1.84 Found: C, 65.03; H, 4.55. (s, 6H, 2,2'-Me of indenyl). US 2010/01 13717 A1 May 6, 2010 81

1894 'C{H} NMR (75 MHz, CDC1): 8 143.0, 138.9, 2H, 1,1'-Hof indenyl), 6.15 (m, 2H, 4,4'-H of furyl), 4.73 (d. 138.1, 137.8, 136.1, 135.6, 132.4, 130.3, 129.9, 129.5, 129.0, J=2.4 Hz, 2H, 3,3'-H), 2.39 (s, 6H, 5,5'-Me of furyl), 2.08 (s, 123.1, 112.7, 111.2, 104.5, 23.3, 22.4, 21.9, 18.4. 6H, 2,2'-Me of indenyl). Example 10g Example 10i 4,4'-Sulfandiyl-bism-2-methyl-7-(2-benzothienyl) 4,4'-Sulfandiyl-bism-2-methyl-7-(5-methyl-thien-2- indenylzirconium dichloride (10i) yl)indenylzirconium dichloride (10g) 1901 Under a nitrogen atmosphere, to a solution of 115 1895 Under a nitrogen atmosphere, in a 16 ml vial mg (0.855 mmol) of benzothiophene in 4 ml of THF, 1.71 ml equipped with PTFE coated stir bar to 1.68 ml of 0.51M (0.86 of 0.5 M(0.855 mmol) of "BuLi in hexanes was added at -80° mmol) of 2-methylthiophene in THF, 1.71 ml of 0.5 M (0.86 C. The resulted mixture was stirred for 3 hours at room mmol) "Bulli in hexanes was added by a dosing pipette with temperature, then cooled to -80° C., and 0.954 ml (0.954 vigorous stirring at -80° C. This mixture was stirred and mmol) of 1.0 M ZnCl2 in THF was added. This mixture was slowly warmed (for ca. 1 hour) to 0°C. Then, 1.88 ml of 0.5 slowly warmed to ambient temperature and additionally M (0.94 mmol) ZnCl2 in THF was added at -80°C., and the stirred for 1 hour at this temperature. The solution of orga obtained mixture was stirred and slowly warmed to ambient nozinc reagent was added to a mixture of 200 mg (0.329 mmol) of 10. Then, 0.825 ml of 0.02 M (0.0165 mmol) temperature and then evaporated to dryness. In a separate 16 Pd(PBus) in THF was added. The cross-coupling reaction ml vial equipped with PTFE coated stir bar containing a was carried out by vigorous stirring for 2 hours at 65°C. Then, mixture of 200 mg (0.33 mmol) of 10, 0.66 ml of 0.02 M this mixture was evaporated to dryness, and 30 ml of toluene (0.013 mmol) Pd(P'Bus), in THF, and 4 ml of THF, the above was added to the residue. This mixture was heated to 110°C., described organozinc reagent was added. This mixture was then evaporated to dryness. To the residue 30 ml of toluene stirred for 4 hours at room temperature, and then evaporated was added, the mixture was heated to 110° C. and filtered to dryness. To the residue, a solution of 1.0 ml of MeSiCls in through Celite 503. The Celite layer was additionally washed 10 ml of dry dichloromethane was added to eliminate an by 2x15 ml of hottoluene. The combined toluene extract was excess of the organozinc reagent. The resulting mixture was evaporated to dryness. The residue was washed by 2x10 ml of stirred at ambient temperature for 1 hour and then evaporated hexanes and dried in vacuum. Yield 175 mg (75%). to dryness. In order to eliminate THF contamination, toluene 1902 Anal. calc. for CHCISZr: C, 60.48; H, 3.38. (20 ml) was added and the mixture was vigorously stirred and Found: C, 60.69; H, 3.47. brought to reflux; then the Suspension was evaporated to 1903 H NMR (300 MHz, CDC1): 8 7.84 (d. J=7.6 Hz, dryness. This procedure was repeated a second time using 60 2H, 5,5'-H of indenyl), 7.76 (d. J–7.6 Hz, 2H, 6,6'-H of ml of toluene, and the resulting Suspension was filtered indenyl), 7.63 (m, 2H, 4/7.4/7'-H in benzothienyl), 7.55 (m, through Celite 503. The resulting toluene filtrate was evapo 2H, 7/4.7/4'-H in benzothienyl), 7.41 (m, 2H, 3,3'-H in ben rated to dryness. The obtained solid was washed with 3x15 ml Zothienyl), 7.32 (m,2H, 5/6.5"/6'-Hinbenzothienyl), 7.24 (m, of hexanes and dried in vacuum. Yield, 181 mg (86%) of a 2H, 6/5.6/5'-H in benzothienyl), 7.05 (m, 2H, 1,1'-Hof inde yellow solid. nyl), 4.85 (m, 2H, 3,3'-H of indenyl), 2.11 (s, 6H, 2,2'-Me of 1896 Anal. calc. for CHCISZr: C, 56.05; H, 3.76. indenyl). Found: C, 55.88; H, 3.85. 1897 H NMR (300 MHz, CDC1): 8 7.63 (d. J–7.5 Hz, Example 10k 2H, 5,5'-Hof indenyl), 7.46 (d. J–3.6 Hz, 3,3'-H of thienyl), 4,4'-Sulfandiyl-bism-2-methyl-7-(2-benzofuryl) 7.35 (d. J–7.5 Hz, 2H, 6,6'-H of indenyl), 6.84 (d. J=2.4 Hz, indenylzirconium dichloride (10k) 2H, 1,1'-H of indenyl), 6.80 (m, 2H, 4,4'-H of thienyl), 4.79 (d. J=2.4 Hz, 2H, 3,3'-H), 2.51 (s, 6H, 5,5'-Me of thienyl), 1904 Under a nitrogen atmosphere, to a solution of 101 2.09 (s, 6H, 2,2'-Me of indenyl). mg (0.855 mmol) of benzofuran in 4 ml of THF, 1.71 ml of 0.5 M (0.855 mmol) of "BuLi in hexanes was added at -80° C. The resulted mixture was stirred for 3 hours at room tempera Example 10h ture, then cooled to -80°C., and 0.954 ml (0.954 mmol) of 1.0 MZnCl2 in THF was added. This mixture was slowly warmed 4,4'-Sulfandiyl-bism-2-methyl-7-(5-methyl-furan to ambient temperature and additionally stirred for 1 hour at 2-yl)indenylzirconium dichloride (10h) this temperature. The solution of organozinc reagent was added to a mixture of 200mg (0.329 mmol) of 10. Then, 0.825 1898 Under a nitrogen atmosphere, following the proce ml of 0.02 M (0.0165 mmol) Pd(PBus), in THF was added. dure described for 10g, 1.41 ml of 0.61 M (0.85 mmol) of The cross-coupling reaction was carried out by vigorous stir 2-methylfuran, 1.71 ml of 0.5 M "BuLi (0.86 mmol), 1.88 ml ring for 2 hours at 65°C. Then, this mixture was evaporated of 0.5 M(0.94 mmol) ZnCl2 in THF, 200 mg (0.33 mmol) of to dryness, and 30 ml oftoluene was added to the residue. This 10, and 0.66 ml of 0.02 M (0.013 mmol) Pd(PBus), in THF mixture was heated to 110°C., then evaporated to dryness. To gave a yellow solid. Yield, 162 mg (81%). the residue 30 ml of toluene was added, the mixture was 1899 Anal. calc. for CHClOSZr: C, 59.00; H, 3.96. heated to 110° C. and filtered through Celite 503. The Celite Found: C, 58.78; H, 4.10. layer was additionally washed by 2x15 ml of hot toluene. The 1900 "H NMR (300 MHz, CDC1): 8 7.65 (d. J=7.6 Hz, combined toluene extract was evaporated to dryness. The 2H, 5,5'-H of indenyl), 7.52 (d. J–7.6 Hz, 2H, 6,6'-H of residue was washed by 2x10 ml of hexanes and dried in indenyl), 6.90 (d. J–3.3 Hz, 3,3'-Hoffuryl), 6.87 (d. J=2.4 Hz, vacuum. Yield 162 mg (72%). US 2010/01 13717 A1 May 6, 2010

1905 Anal. calc. for CHClOSZr: C, 63.33; H, 3.54. 1912 H NMR (300 MHz, CDC1): 8 7.85-7.94 (m, 4H, Found: C, 63.51; H, 3.66. 2,2',4,4'-H in CHCF), 7.77 (d. J=7.3 Hz, 2H, 5,5'-H of 1906 H NMR (300 MHz, CDC1): 8 7.84 (d. J=7.6 Hz, indenyl), 7.55-7.67 (m, 4H, 5.5',6,6'-H in CHCF), 7.26 (d. 2H, 5,5'-H of indenyl), 7.77 (d. J=7.6 Hz, 2H, 6,6'-H of J–7.3 Hz, 2H, 6,6'-H of indenyl), 6.53 (m, 2H, 1,1'-H of indenyl), 7.63 (m,2H,4/7.4/7'-Hinbenzofuryl), 7.55 (m,2H, indenyl), 4.84 (m. 2H, 3,3'-Hof indenyl), 2.10 (s, 6H, 2,2'-Me 7/47/4'-Hinbenzofuryl), 7.42 (m,2H,3,3'-Hinbenzofuryl), of indenyl). 7.32 (m, 2H, 5/6.5/6'-H in benzofuryl), 7.24 (m, 2H, 6/5.6/ 5'-H in benzofuryl), 7.05 (m,2H, 1,1'-Hof indenyl), 4.86 (m, Example 10n 2H, 3,3'-H of indenyl), 2.12 (s, 6H, 2,2'-Me of indenyl). 4,4'-Sulfandiyl-bism-2-methyl-7-(2,5-dimethylphe Example 101 nyl)indenylzirconium dichloride (10n) 1913 Under a nitrogen atmosphere in a 16 ml vial 4,4'-Sulfandiyl-bism-2-methyl-7-(4-fluorophenyl) equipped with PTFE coated stir bar and containing 8.80 ml of indenylzirconium dichloride (101) 0.25 M (2.20 mmol) ZnCl, in THF, 2.0 ml of 1.0 M (2.00 1907 Under a nitrogen atmosphere, to a mixture of 0.954 mmol) 2.5-dimethylphenylmagnesium bromide in THF was ml (0.954 mmol) of 1.0 M ZnCl, in THF and 4 ml of THF added at room temperature. This mixture was stirred for 1 0.725 ml of 1.18 M (0.855 mmol), para-fluorophenylmagne hour. Then, in a separate 16 ml vial equipped with PTFE sium bromide in THF was added. This mixture was stirred for coated stir bar and containing a suspension of 150 mg (0.25 mmol) of 10 in 4.0 ml of THF, 3.40 ml of the solution of the 1 hour at room temperature. The resulted white suspension above obtained organozinc reagent and 0.50 ml of 0.02 M was added to 200 mg (0.329 mmol) of 10 in 3 ml of THF. (0.010 mmol) Pd(P'Bus), in THF were added by a dosing Then, 0.825 ml of 0.02 M (0.0165 mmol) Pd(PBus), in THF pipette. The reaction mixture was stirred for 3 hours at 70° C. was added. The cross-coupling reaction was carried out by and then evaporated to dryness. To the residue, a solution of vigorous stirring for 2 hours at 70°C. Then, this mixture was 1.0 ml of MeSiCl, in 10 ml of dry dichloromethane was added evaporated to dryness, and 30 ml of toluene was added to the to eliminate an excess of the organozinc reagent. The resulted residue. This mixture was heated to 110°C., then evaporated mixture was stirred at ambient temperature for 1 hour and to dryness. To the residue 30 ml of toluene was added, the then evaporated to dryness. In order to eliminate THF con mixture was heated to 110° C. and filtered through Celite 503. tamination, the residue was treated with hot toluene (20 ml), The Celite layer was additionally washed by 2x15 ml of hot then, the suspension was evaporated to dryness. The residue toluene. The combined toluene extract was evaporated to was additionally treated with 60 ml of hot toluene, and the dryness. The residue was washed by 2x10 ml of hexanes and resulted suspension filtered through Celite 503. The toluene dried in vacuum. Yield 175 mg (83%). extract was evaporated to dryness. The obtained solid was 1908 Anal. calc. for CHClFSZr: C, 60.17; H, 3.47. washed with 3x15 ml of hexanes and dried in vacuum. Yield Found: C, 60.35; H, 3.56. 130 mg (80%) of yellowish solid. 1909 H NMR (300 MHz, CDC1): 8 7.73 (d. J=7.3 Hz, 1914 Anal. calc. for CHCISZr: C, 65.63; H, 4.90. 2H, 5,5'-H of indenyl), 7.64 (m, 4H, 2,2',6,6'-H of CHF), Found: C, 65.81; H, 5.00. 7.20 (d. J–7.3 Hz, 2H, 6,6'-H of indenyl), 7.14 (m, 4H, 3,3', 1915 H NMR (CDC1): 87.72 (d. J–7.3 Hz, 2H, 5,5'-H 5,5'-H of CHF), 6.55 (d. J=2.5 Hz, 2H, 1,1'-H of indenyl), in indenyl), 7.05-7.20 (m, 8H, 6,6'-H in indenyl and 3,3'44'. 4.80 (d. J=2.5 Hz,2H,3,3'-Hof indenyl), 2.09 (s, 6H, 2,2'-Me 6,6'-H in 2.5-MeCH), 6.25 (brs, 2H, 1,1'-H in indenyl), of indenyl). 4.80 (d. J=2.4 Hz, 2H,3,3'-Hin indenyl), 2.31 (s, 6H, 5,5'-Me in 2.5-MeCH), 2.11 (s, 6H, 2,2'-Mein indenyl), 2.10 (brs, Example 10m 6H, 2,2'-Me in 2.5-MeCH). 4,4'-Sulfandiyl-bism-2-methyl-7-(3-trifluorometh ylphenyl)indenylzirconium dichloride (10m) Example 10o 4,4'-Sulfandiyl-bism-2-methyl-7-(4-biphenyl)inde 1910 Under a nitrogen atmosphere, to a mixture of 0.954 nylzirconium dichloride (10o) ml (0.954 mmol) of 1.0 M ZnCl in THF and 4 ml of THF 0.838 ml of 1.02 M (0.855 mmol), meta-trifluoromethylphe 1916. Under a nitrogen atmosphere in a 16 ml vial nylmagnesium bromide in THF was added. This mixture was equipped with PTFE coated stir bar and containing 8.80 ml of stirred for 1 hour at room temperature. The resulted white 0.25 M (2.20 mmol) ZnCl in THF, 2.0 ml of 1.0 M (2.00 suspension was added to 200 mg (0.329 mmol) of 10 in 3 ml mmol) 4-biphenylmagnesium bromide in THF was added at of THF. Then, 0.825 ml of 0.02 M(0.0165 mmol) Pd(P'Bus), room temperature. This mixture was stirred for 1 hour. Then, in THF was added. The cross-coupling reaction was carried in a separate 16 ml vial equipped with PTFE coated stir bar out by vigorous stirring for 2 hours at 70° C. Then, this and containing a suspension of 150 mg (0.25 mmol) of 10 in mixture was evaporated to dryness, and 30 ml of toluene was 4.0 ml of THF, 3.40 ml of the solution of the above obtained added to the residue. This mixture was heated to 110°C., then organozinc reagent in THF and 0.50 ml of 0.02 M (0.010 evaporated to dryness. To the residue 30 ml of toluene was mmol) Pd(PBus) in THF were added by a dosing pipette. added, the mixture was heated to 110°C. and filtered through The reaction mixture was stirred for 3 hours at 70° C. and then Celite 503. The Celite layer was additionally washed by 2x15 evaporated to dryness. To the residue, a solution of 1.0 ml of ml of hot toluene. The combined toluene extract was evapo MeSiCl, in 10 ml of dry dichloromethane was added to elimi rated to dryness. The residue was washed by 2x10 ml of nate an excess of the organozinc reagent. The resulted mix hexanes and dried in vacuum. Yield 160 mg (66%). ture was stirred at ambient temperature for 1 hour and then 1911 Anal. calc. for CHClFSZr: C, 55.28; H, 3.00. evaporated to dryness. In order to eliminate THF contamina Found: C, 55.12; H, 3.09. tion, the residue was treated with hottoluene (20 ml), then, the US 2010/01 13717 A1 May 6, 2010

Suspension was evaporated to dryness. The residue was addi mmol) p-tolylmagnesium bromide in THF was added by a tionally treated with 60 ml of hot toluene, and the resulted dosing pipette to a mixture of 0.86 ml of 0.5 M (0.43 mmol) suspension filtered through Celite 503. The toluene extract ZnCl2 in THF and 3 ml of THF by vigorous stirring at ambient was evaporated to dryness. The obtained solid was washed temperature. This organozinc reagent was additionally stirred with 3x15 ml of hexanes and dried in vacuum. Yield 140 mg for 1 hour and then added to a mixture of 150 mg (0.30 mmol) (75%) of yellowish solid. of 11, 0.30 ml of 0.02 M (0.006 mmol) Pd(P'Bus), in THF, 1917. Anal. calc. for CHCISZr: C, 70.00; H, 4.27. and 3 ml of THF placed in a separate 16 ml vial equipped with Found: C, 70.29; H, 4.36. a PTFE coated stir bar. The reaction mixture was stirred for 20 1918 H NMR (CDC1): 87.28-7.80 (m. 22H, 5.5',6,6'-H hours at room temperature and then evaporated to dryness. in indenyls and 4-biphenyls), 6.67 (d. J=2.4 Hz, 2H, 1,1'-H in The product was extracted with 3x30 ml of hot hexanes. The indenyl), 4.85 (d. J=2.4 Hz, 2H, 3,3'-H in indenyl), 2.12 (s. extract was filtered through Celite 503 and then evaporated to 6H, 2,2'-Me in indenyl). dryness. The residue was dried in vacuum. Yield 139 mg Examples 11a–11r (91%) of yellowish solid. Negishi coupling applying dimethylsilyl(m-2-me 1925. Anal. calc. for CHCl, NSi Zr: C, 54.20; H, 5.73. thyl-4-bromoinden-1-yl)-(m-tert-butylamido)Zirco Found: C, 54.38: H, 5.80. nium dichloride (11) 1926) "H NMR (CDC1): 87.70 (m. 1H, 5-H in indenyl), 1919 7.45 (m. 2H, 2,6-H in p-tolyl), 7.29 (m. 2H,3,5-H in p-tolyl), 7.18-7.27 (m, 2H, 6,7-H in indenyl), 6.99 (m. 1H, 3-H in indenyl), 2.40 (s.3H, 4-Me in p-tolyl), 2.36 (s.3H, 2-Me in Br R indenyl), 1.33 (s, 9H, Bu), 0.88 (s, 3H, SiMeMe'), 0.71 (s, 3H, SiMeMe'). RZnCl 1927 C{H} NMR (CDC1,): & 142.0, 139.7, 139.6, Pd(PBus) 138.1, 137.7, 136.6, 134.7, 131. 1, 129.7, 129.2, 127.6, 125.3, THF 114.6, 58.1, 34.4, 22.6, 19.8, 7.9, 7.1. Mes V AC2 MesV /AC2 Example 11c NBu NBu Dimethylsilyl(m-2-methyl-4-m-tolylinden-1-yl)(m- 11 11a-11r tert-butylamido)Zirconium dichloride (11c) R= Me (11a), 4-MeC6H4 (11b), 3-MeC6H4 (11c), 2-Me-C6H4 (11d), 2,4,6-MeC6H2 (11e), 2.5-MeOH (11f), 4-FCH (11g), 3-CFCH (11h), 4-PhCH4 (11i), 4 Me2NC6H4 (11k), 2-MeOC6H4 (111), 3-methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl 1928. Following the procedure described for 11b, 0.39 ml (11 m), 5-methyl-2-furyl (11n), 5-methyl-2-thienyl (11o), 2-benzothienyl (11p), 2 of 1.0 M (0.39 mmol) m-tolylmagnesium bromide in THF benzofuryl (11r) gave yellowish solid. Yield 143 mg (93%). 1929 Anal. calc. for CHCl, NSi Zr: C, 54.20; H, 5.73. Found: C, 54.39; H, 5.68. Example 11a 1930 "H NMR (CDC1): 8 7.71 (m, 1H, 5-H in indenyl), Dimethylsilyl(m-2,4-dimethylinden-1-yl)(m-tert 7.34-7.39 (m, 3H, 2.5,6-H in m-tolyl), 7.20-7.29 (m, 3H, butylamido)Zirconium dichloride (11a) 6.7-H in indenyl and 4-H in m-tolyl), 7.00 (bris, 1H, 3-H in 1920. In a nitrogen atmosphere Glovebox, in a 16 ml vial indenyl), 2.41 (s.3H, 3-Me in m-tolyl), 2.37 (m, 3H, 2-Me in equipped with a PTFE coated stir bar and containing a sus indenyl), 1.33 (s, 9H, Bu), 0.88 (s, 3H, SiMeMe'), 0.71 (s, pension of 200mg (0.40 mmol) of 11 in 10.0 ml of THF, 0.265 3H, SiMeMe'). ml of 2.0 M MeZnC1 (0.52mmol) in THF and 0.40 ml of 0.02 M (0.008 mmol) Pd(PBus) in THF were added by a dosing Example 11d pipette. The reaction mixture was stirred for 20 hours at room temperature and then evaporated to dryness. The product was Dimethylsilyl(m-2-methyl-4-o-tolylinden-1-yl)(m- extracted with 3x30 ml of hot hexanes. The extract was fil tert-butylamido)Zirconium dichloride (11d) tered through Celite 503 and then evaporated to dryness. The 1931. Following the procedure described for 11b, 0.47 ml residue was dried in vacuum. Yield 120 mg (69%) of yellow of 0.83 M (0.39 mmol) o-tolylmagnesium bromide in THF ish solid. gave yellowish solid. Yield 143 mg (93%). 1921 Anal. calc. for CHC1, NSi Zr: C, 47.09: H, 5.81. 1932 Anal. calc. for CHCl, NSi Zr: C, 54.20; H, 5.73. Found: C, 47.21; H, 5.76. 1922 "H NMR (CDC1): 87.56 (m. 1H, 5-H in indenyl), Found: C, 54.41; H, 5.70. 7.10 (dd, J=8.5 Hz, J=6.9 HZ, 1H, 6-H in indenyl), 7.03 (m, 1933 H NMR (CDC1): 87.74 (d. J=8.5 Hz, 1H, 5-H in 1H, 7-H in indenyl), 6.88 (m. 1H, 3-Hin indenyl), 2.46 (s.3H, indenyl), 7.17-7.33 (m, 6H, 6,7-H in indenyl and 3,4,5,6-H in 4-Mein indenyl), 2.39 (m, 3H, 2-Mein indenyl), 1.31 (s, 9H, o-tolyl), 7.13 (m. 1H, 3-H in indenyl), 2.33 (S. 3H, 2-Me in 'Bu), 0.84 (s, 3H, SiMeMe'), 0.69 (s.3H, SiMeMe'). indenyl), 2.11 (brs, 3H, 2-Me in o-tolyl), 1.33 (s, 9H, Bu), 1923) 'C{H} NMR (CDC1): & 142.5, 135.4 (two reso 0.89 (s.3H, SiMeMe'), 0.71 (s.3H, SiMeMe'). nances), 135.2, 132.1, 128.0, 126.3, 122.7, 112.3, 56.8, 33.2, 19.6, 18.6, 6.1, 5.8. Example 11e Example 11b Dimethylsilyl(m-2-methyl-4-mesitylinden-1-yl)(m- Dimethylsilyl(m-2-methyl-4-p-tolylinden-1-yl)(m- tert-butylamido)Zirconium dichloride (11e) tert-butylamido)Zirconium dichloride (11b) 1934 Following the procedure described for 11b, 0.44 ml 1924. In a nitrogen atmosphere Glovebox, in a 16 ml vial of 0.88 M (0.39 mmol) mesitylmagnesium bromide in THF equipped with a PTFE coated stir bar, 0.39 ml of 1.0 M (0.39 gave yellowish solid. Yield 159 mg (98%).

US 2010/01 13717 A1 May 6, 2010

1977 "C{H} NMR (CDC1,): & 1564, 155.8, 144.7, Example 13i2 144.6, 136.6, 130.5, 128.6, 128.3, 127.0, 126.6, 126.1, 124.8, Suzuki-Miyaura reaction of metallocene 13 to pro 122.8, 122.0, 115.0, 112.8, 106.2, 58.2, 34.3, 19.8, 7.3, 7.0. duce rac-dimethylsilyl-bis(m-4-phenyl-6-isopropyl 2,5-dimethylinden-1-yl)Zirconium dichloride (13i) Example 12a 1982 Negishi reaction of metallocene 12 to produce dim Br ethylsilyl(m-tetramethylcyclopentadienyl)(m-4- methyl-2,6-diisopropylphenyl)Zirconium dichloride (12a) NaBPhi, Pd(PBus) 1978 toluene, 90° C. Cl2Zr SiMe ---

B Ph -Cl ZrS RZnCl MeSi C Pd(P Bus) N --THF N iPr iPr ClZi SiMe2

Br Ph 12 1983. In a 16 ml vial equipped with PTFE coated stir bar, to a solution of 92 mg (0.14 mmol) of 13 in 10 ml of toluene, 105 mg (0.31 mmol) of NaBPha, and 0.28 ml (0.0056 mmol) of 0.02 M solution of Pd(PBus), in toluene were added. The reaction mixture was stirred for 20h at 90° C. The reaction mixture was cooled to ambient temperature and filtered through a glass frit (G4). The filtrate was evaporated to dry 1. C ness. The residue was washed with 2x15 ml of hot hexanes and dried in vacuum. Yield 66 mg (72%) of orange solid. MeSi 1984 Anal. calc. for CHClSiZr: C, 65.83; H, 5.22. N u1 ZS Found: C, 66.01; H, 5.28. N 1985 H NMR (CDC1): 8 7.55 (m, 2H, 6,6'-H in inde iPr iPr nyls), 7.17-7.50 (m. 10H, Phand Ph'), 6.99 (d. J=9.0 Hz, 2H, 7.7'-H in indenyls), 6.39 (s. 2H, 3,3'-H in indenyls), 2.27 (s. 6H, 2,2'-Me), 2.18 (s, 6H, 5,5'-Me), 1.30 (s, 6H, SiMe...). Example 15a2 Suzuki-Miyaura reaction of metallocene 15 to pro R duce rac-dimethylsilyl-bis(m-4-phenyl-6-isopropyl 12a 2-methylinden-1-yl)Zirconium dichloride (15a) 1986 R = Me (12a) Br 1979. Following the procedure described for 11a, 200 mg (0.34 mmol) of 12 in 4 ml of THF, 0.22 ml of 2.0 M (0.44 mmol) MeZnClin THF, and 0.35 ml of 0.02 M (0.007 mmol) NaBPhi, Pd(PBus) Pd(P'Bus), in THF gave yellowish solid. Yield 117 mg (66%). toluene, 90° C. 1980 Anal. calc. for CHCl, NSi Zr: C, 54.41; H, 7.04. Cl2Zr SiMe Found: C, 54.60; H, 7.17. 1981 H NMR (CDC1): 8 6.91 (q, J=0.6 Hz, 2H,3,5-H in CH), 3.30 (sept, J=6.7 Hz, 2H, CHMe), 2.34 (s, 6H, 3.4-Mein CMe), 2.28 (t, J–0.6 Hz, 3H, 4-Mein CH), 2.23 (s, 6H, 2.5-Mein CMe), 1.22 (d. J=6.7 Hz, 6H, CHMeMe'), B 1.08 (d. J=6.7 Hz, 6H, CHMeMe'), 0.63 (s, 6H, SiMe). US 2010/01 13717 A1 May 6, 2010 87

purchased from Aldrich Chemical Company, and a 500 cc -continued column packed with dried 5 A mole sieves purchased from Ph Aldrich Chemical Company. 1996 Polymerization grade propylene was used without further purification. 1997 MAO (methylalumoxane, 10 wt % in toluene) was purchased from Albemarle Corporation and was used as a 1 Cl2Zr, SiMe2 wt % or 2 wt % in toluene solution. Micromoles of MAO reported in the experimental section are based on the micro moles of aluminum in MAO. The formula weight of MAO is 58.0 grams/mole. 1998 Reactor Description and Preparation: Polymeriza tions were conducted in an inert atmosphere (N2) drybox Ph using autoclaves equipped with an external heater for tem perature control, glass inserts (internal Volume of reac 1987. In a 16 ml vial equipped with PTFE coated stir bar, tor=23.5 mL for C2 and C2/C8 runs; 22.5 mL for C3 and to a solution of 100 mg (0.14 mmol) of 15 in 10 ml of toluene, C2/C3 runs), septum inlets, regulated Supply of nitrogen, 105 mg (0.31 mmol) of NaBPh, and 0.28 ml (0.0056 mmol) ethylene and propylene, and equipped with disposable PEEK of 0.02 M solution of Pd(PBus), in toluene were added. The mechanical stirrers (800 RPM). The autoclaves were pre reaction mixture was stirred for 20h at 90° C. The reaction pared by purging with dry nitrogen at 110°C. or 115°C. for mixture was cooled to ambient temperature and filtered 5 hours and then at 25°C. for 5 hours. through a glass frit (G4). The filtrate was evaporated to dry 1999 Ethylene Polymerization or Ethylene/1-octene ness. The product was extracted from the residue with 4x25 Copolymerization. The reactor was prepared as described ml of hexanes. The combined filtrate was evaporated to dry above, and then purged with ethylene. Toluene, 1-octene (100 ness, and the residue was dried in vacuum. Yield 73 mg (73%) uL when used), and activator (MAO) were added via syringe of orange Solid. at room temperature and atmospheric pressure. The reactor was then brought to process temperature (80°C.) and charged 1988 Anal. calc. for CHClSiZr: C, 67.38: H, 5.94. with ethylene to process pressure (75 psig=618.5 kPa) while Found: C, 67.66; H, 6.10. stirring at 800 RPM. The TMC (0.02 umol, unless indicated 1989 HNMR (CDC1): 87.29-7.71 (m. 14H, 5,5,7,7-H otherwise) was added via Syringe with the reactor at process in indenyls and Ph, Ph'), 6.87 (s.2H, 3,3'-H in indenyls), 2.93 conditions. Amounts of reagents not specified above are given (m. 2H, CHMe in both indenyls), 2.26 (s, 6H, 2,2'-Me in in Tables a and c. Ethylene was allowed to enter (through the indenyls), 1.26 (m. 12H, CHMe in both indenyls). use of computer controlled solenoid valves) the autoclaves 1990 While the present invention has been described and during polymerization to maintain reactor gauge pressure illustrated by reference to particular embodiments, those of (+/-2 psig). Reactor temperature was monitored and typically ordinary skill in the art will appreciate that the invention lends maintained within +/-1° C. Polymerizations were halted by itself to variations not necessarily illustrated herein. For this addition of approximately 50 psid O/Ar (5 mole % O2) gas reason, then, reference should be made solely to the appended mixture to the autoclaves for approximately 30 seconds. The claims for purposes of determining the true scope of the polymerizations were quenched after a predetermined cumu present invention. lative amount of ethylene had been added or for a maximum of 20 minutes polymerization time. The final conversion (in Experimental Polymerizations psi) of ethylene added/consumed is reported in the Tables a 1991. In the following experiments pressure is reported in and c, in addition to the quench time for each run. The reactors atmospheres and pounds per square inch. The conversion were cooled and vented. The polymer was isolated after the factors to S.I. Units are: 1 psi equals 6.894757 kPa and 1 atm solvent was removed in-vacuo. Yields reported include total equals 101.325 kPa. weight of polymer and residual catalyst. 1992 Transition metal compound (TMC) solutions were 2000 Propylene Polymerization. The reactor was pre typically prepared using toluene (ExxonMobil Chemical pared as described above, then heated to 40° C. and then anhydrous, stored under N) (98%). Unless otherwise men purged with propylene gas at atmospheric pressure. Hexanes, tioned, TMC solutions are 0.2 mmol/L for C, and C/Cs MAO, and liquid propylene (1.066 mL, unless indicated oth (co)polymerizations, and 0.6 mmol/L for C and C/C (co) erwise in Table e) were added via syringe. The reactor was polymerizations. then heated to process temperature (70° C.) while stirring at 800 RPM. The TMC was added via syringe with the reactor at 1993 Solvents, polymerization grade toluene and hexanes process conditions. Amounts of reagents not specified above were supplied by ExxonMobil Chemical Co. and thoroughly are given in Table e. Reactor temperature was monitored and dried and degassed prior to use. typically maintained within +/-1° C. Polymerizations were 1994 1-octene (98%) was purchased from Aldrich halted by addition of approximately 50 psid O/Ar (5 mole% Chemical Company and dried by stirring over NaK overnight O) gas mixture to the autoclaves for approximately 30 sec followed by filtration through basic alumina (Aldrich Chemi onds. The polymerizations were quenched based on a prede cal Company, Brockman Basic 1). termined pressure loss of approximately 5 psid. The actual 1995 Polymerization grade ethylene was used and further quench time is reported in Table e for each run. The reactors purified by passing it through a series of columns: 500 cc were cooled and vented. The polymer was isolated after the Oxyclear cylinder from Labelear (Oakland, Calif.) followed solvent was removed in-vacuo. Yields reported include total by a 500 cc column packed with dried 3 A mole sieves weight of polymer and residual catalyst. Catalyst activity is US 2010/01 13717 A1 May 6, 2010 reported as grams of polymer per mmol transition metalcom second step involves running a high-resolution scan protocol pound per hour of reaction time (g/mmol.hr). to measure the second melt of the sample. The protocol heats 2001 Ethylene/Propylene Copolymerization. The reactor each cell from 27° C. to 200° C. in -3 minutes and then was prepared as described above, and then purged with eth rapidly cools the sample to room temperature. The high ylene. Reactors were heated to 40°C. and ethylene was then resolution scan takes approximately three times the amount added to the reactor to a target pressure of 10 psig (single of time to complete as the rapid-scan protocol. If multiple addition), followed by the addition of hexanes, MAO, and melting peaks are present, EpochR Software reports the larg then liquid propylene (1.066 mL). All additions were made estamplitude peak. SAMMS data is reported under the head via Syringe. The reactor was then heated to process tempera ing of Tm (C.) in Tables b and d. ture (70° C.) while stirring at 800 RPM. The TMC was added 2006 For propylene homopolymers, the thermal analysis via Syringe with the reactor at process conditions. Amounts of was performed using a 1290 TA Instruments Differential reagents not specified above are given in Table g. Reactor Scanning Calorimeter (DSC) by first heating the sample from temperature was monitored and typically maintained within 25° C. to 220° C. at 10°C/min, holding the temperature at +/-1° C. Polymerizations were halted by addition of approxi 220°C. for 5 minutes, then cooling at 10°C./min from 220 mately 50 psid O/Ar (5 mole % O.) gas mixture to the C. to 25° C., and finally again heating to 220° C. at 10° autoclaves for approximately 30 seconds. The polymeriza C./min. The second heat results have been reported under the tions were quenched based on a predetermined pressure loss heading of DSC (C.) in Table f. A value of zero indicates that of approximately 5 psid. The actual quench time is reported in the polymer had no melting point. Multiple numbers indicate Table g for each run. The reactors were cooled and vented. a polymer with more than one melting point. The heat of The polymer was isolated after the solvent was removed fusion, delta H, is also recorded in Table f. in-vacuo. Yields reported include total weight of polymer and 2007 Samples for infrared analysis were prepared by residual catalyst. depositing the stabilized polymer Solution onto a silanized 2002 Polymer characterization. Polymer characterization wafer (Part number S10860, Symyx). By this method, results for polyethylene samples are reported in Table b, for approximately between 0.12 and 0.24 mg of polymer is ethylene-1-octene copolymers are reported in Table d, for deposited on the wafer cell. The samples were subsequently polypropylene samples are reported in Table f, and for ethyl analyzed on a Brucker Equinox 55 FTIR spectrometer ene-propylene copolymers are reported in Table h. equipped with Pikes's MapplR specular reflectance sample 2003 For analytical testing, polymer sample solutions accessory. Spectra, covering a spectral range of 5000 cm to were prepared by dissolving polymer in 1,2,4-trichloroben 500cm, were collected at a 2 cm' resolution with 32 scans. Zene (TCB, 99-96 purity from Sigma-Aldrich) containing 2008 For ethylene-1-octene copolymers, the wt. '% 2,6-di-tert-butyl-4-methylphenol (BHT, 99% from Aldrich) copolymer is determined via measurement of the methyl at 160° C. in a shaker oven for approximately 3 hours. The deformation band at 1375 cm. The peak height of this band typical concentration of polymer in Solution is between 0.4 to is normalized by the combination and overtone band at 4321 0.9 mg/mL with a BHT concentration of 1.25 mg BHT/mL of cm', which corrects for path length differences. The normal TCB. Samples are cooled to 135° C. for testing. ized peak height is correlated to individual calibration curves 2004 Molecular weights (weight average molecular from "H NMR data to predict the wt.% copolymer content weight (Mw) and number average molecular weight (Mn)) within a concentration range of -2 to 35 wt.% for octene. and molecular weight distribution (MWD-Mw/Mn), which Typically, R correlations of 0.98 or greater are achieved. is also sometimes referred to as the polydispersity (PDI) of These numbers are reported in Table d under the heading, the polymer, were measured by Gel Permeation Chromatog Octene wt %). raphy using a Symyx Technology GPC equipped with evapo 2009 For ethylene-propylene copolymers, the wt.% eth rative light scattering detector and calibrated using polysty ylene is determined via measurement of the methylene rock rene standards (Polymer Laboratories: Polystyrene ing band (-770 cm to 700 cm). The peak area of this band Calibration Kit S-M-10: Mp (peak Mw) between 5000 and is normalized by sum of the band areas of the combination 3,390,000). Samples were run in TCB at (135° C. sample and overtone bands in the 4500 cm to 4000 cm range. The temperatures, 160° C. oven/columns) using three Polymer normalized band area is then correlated to a calibration Laboratories: PLgel 10um Mixed-B300x7.5 mm columns in curved from C NMR data to predict the wt.% ethylene series. No column spreading corrections were employed. within a concentration range of -5 to 40 wt.%. Typically, R Numerical analyses were performed using EpochR software correlations of 0.98 or greater are achieved. These numbers available from Symyx Technologies. are reported in Table hunder the heading, Ethylene (wt %). 2005. The sample preparation for SAMMS (Sensory 2010 For propylene homo-polymers, an infrared spec Array Modular Measurement System) thermal analysis mea troscopy-based partial least-squares (PLS) model was devel Surements involved depositing the stabilized polymer Solu oped for predicting an IR tacticity index, reported as an esti tion onto a silanized wafer (Part Number S10457. Symyx). mated Tm, for isotactic polypropylene (iPP). The model was The solvent was then evaporated off at ~145° C. By this built using PLSplus/IQ add-on application to the Grams/AI method, approximately between 0.12 and 0.24 mg of polymer (Version 7.00) software from ThermoGalactic. The model is is deposited onto each corresponding wafer cell. Thermal based on a training set consisting of IR spectra of iPP Samples analysis was measured on a Symyx Technologies SAMMS with known Tm values spanning a range of ~100° C. to ~166° instrument that measures polymer melt temperatures via the C. The iPPs were prepared in lab and commercial reactors 3(1) technique. The analysis first employs a rapid-scan proto using metallocene and Zieglar-Natta catalyst systems. Their col that heats each cell from 27°C. to 200° C. in ~35 seconds average Mw ranged from 157 k to 436 k. Their IR spectra and then rapidly cools the sample to room temperature. This were collected from Solution cast films Supported on gold complete procedure takes approximately 60 seconds per cell coated silicon wafers via a Bruker Equinox 55 FTIR spec and is used to minimize each sample's thermal history. The trometer with a Pike MapplR specular reflectance sample

US 2010/01 13717 A1 May 6, 2010 96

inconsistent with this text. Likewise, the term “comprising is considered synonymous with the term “including for pur poses of Australian law. Parth: Ethylene-Propylene Polymerization Runs - Part 2. Ethylene Exhi TMC Mw Mn PDI (wt.%) What we claim is: EP-1 Oa. 92,503 55.432 7 35.9 1. A substituted metallocene compound prepared by the EP-2 Oa. 71.232 35,791 2.0 3O.S process comprising: EP-3 Oa. 41,728 22,993 8 2S.O (a) providing a first compound represented by the formula EP-4 Oa. 96.435 52,601 8 3O.S EP-5 Ob 167,275 99,785 7 23.4 (1): EP-6 Ob 161,430 96,226 7 21.O AMX, EP-7 Ob 152,791 86,618 8 18.7 EP-8 Ob 135,789 79,606 7 21.5 wherein: EP-9 Oc 150,338 87,012 7 20.4 EP-10 Oc 128,583 71,785 8 19.3 M is a transition metal atom having a coordination number EP-11 Oc 160,233 96.920 7 24.4 of n selected from Group 3, 4, 5 or 6 of the Periodic Table EP-12 Oc 166,938 96,667 7 21.7 of Elements, or a lanthanide metal atom, or actinide EP-13 Od 245,783 129,894 9 27.4 EP-14 Od 265,550 145,750 8 15.3 metal atom; EP-15 Od 248,086 137,237 8 13.4 n is 2, 3, 4, 5 or 6: EP-16 Od 233,468 116,849 2.0 24.1 A is a monocyclic or polycyclic ligand that is pi-bonded to EP-17 Oe 67,171 102,897 .6 30.4 EP-18 Oe 46,180 89,061 .6 28.3 M and is substituted with at least one halogen or sul EP-19 Oe 66.462 101,838 .6 28.3 fonate substituent directly bonded to any sp carbon EP-2O Oe 66.421 101,623 .6 29.6 atom at a bondable ring position of the ligand; and EP-21 Of 38,351 18,365 2.1 29.5 EP-22 Of 34,493 16,812 2.1 29.8 each X is, independently, a univalent anionic ligand, or two EP-23 Of O2,647 28,681 3.6 32.9 X are joined and bound to the metal atom to form a EP-24 Of 55,577 38,961 4.0 32.O metallocycle ring, or two X are joined to form a chelat EP-25 Oh 21,471 74,298 1.6 36.4 ing ligand, a diene ligand, or an alkylidene ligand; and EP-26 Oh 16,565 71451 1.6 30.3 EP-27 Oh O4,377 40,264 2.6 (b) reacting said first compound with a transfer-agent EP-28 Oh 44,029 88,986 1.6 36.3 which comprises a hydrocarbyl, Substituted hydrocar EP-29 O 209,496 128,180 1.6 29.7 byl, halocarbyl, substituted halocarbyl, silylcarbyl, or EP-30 O 220,137 127,869 1.7 29.3 germylcarbyl radical capable of replacing the halogen or EP-31 O 52,017 70,633 2.2 34.2 EP-32 O 47,835 65,455 2.3 34.5 Sulfonate Substituent of ligand A under reaction condi EP-33 Om 78,450 103,865 1.7 31.1 tions in the presence of a coupling catalyst. EP-34 Om 73,346 102,022 1.7 29.6 EP-35 Om 71,117 98,578 1.7 31.0 2. The substituted metallocene compound of claim 1 EP-36 Om 76,799 104.293 1.7 33.7 wherein A comprises a Substituted monocyclic arenyl ligand EP-37 rac-8b 97,757 32,041 3.1 1.5% or Substituted polycyclic arenyl ligand. EP-38 rac-8b 19,090 49,673 2.4 S.1 3. The substituted metallocene compound of claim 1 EP-39 rac-8d 50,272 29,411 S.1 0.8% EP-40 rac-8d 71,902 40,665 4.2 3.5% wherein A comprises a halogenated cylopentadienyl, haloge EP-41 rac-8d 55,528 33,494 4.6 2.6* nated indenyl, or halogenated fluorenyl group, and the halo EP-42 rac-8d 61,742 43,723 3.7 2.6* gen Substituent of ligand A is a bromo Substituent. EP-43 rac-8f 51417 87.225 7 EP-44 rac-8f 72,095 100,623 7 12.5 4. The substituted metallocene compound of claim 1 EP-45 rac-8f 36,096 72,505 9 2.7% wherein said A is a substituted cyclopentadienyl, substituted EP-46 rac-8f 33,308 67,200 2.0 2.9* heterocyclopentadienyl, substituted indenyl, substituted het EP-47 rac-8g 23,392 36,415 3.4 9.2 eroindenyl, substituted fluorenyl, substituted heterofluorenyl, EP-48 rac-8g 36,284 45,206 3.0 13.1 EP-49 rac-9b 71,060 42,965 7 13.1 Substituted cyclopentanaphthyl, Substituted heterocyclopen EP-50 rac-9b 78.476 49,506 .6 15.9 tanaphthyl, substituted heterophenyl, substituted heterocy EP-51 rac-9b 57,338 32,830 7 14.5 clopentapentalenyl, Substituted heterocyclopentaindenyl, or EP-52 rac-9b 58,897 33,275 8 11.3 Substituted heterobenzocyclopentaindenyl ligand. EP-53 rac-9c 59,262 30,994 9 6.3 EP-54 rac-9c 58,433 33,550 7 8.9 5. The substituted metallocene compound of claim 1 EP-55 rac-9d 70,356 38,566 8 17.7 wherein the halogen or Sulfonate Substituent of ligand A is a EP-56 rac-9d 76,257 46,721 .6 24.1 EP-57 rac-9e 63,322 33,469 9 10.2 chloro, bromo, iodo, tosylate or triflate substituent. EP-58 rac-9e 67,161 40,098 7 6.8 6. The substituted metallocene compound of claim 1 wherein ligand A is a halogenated cyclopentadienyl, haloge **Outside FTIR calibration range of 5.14 to 38.79 wt % ethylene. nated indenyl, or halogenated fluorenyl group, and the halo 2011 While the present invention has been described and gen Substituent of ligand A is a chloro or bromo Substituent. illustrated by reference to particular embodiments, those of 7. The substituted metallocene compound of claim 1 ordinary skill in the art will appreciate that the invention lends wherein M is titanium, Zirconium or hafnium. itself to variations not necessarily illustrated herein. For this 8. The substituted metallocene compound of claim 1 reason, then, reference should be made solely to the appended wherein the transfer-agent is an organometallic compound. claims for purposes of determining the true scope of the 9. The substituted metallocene compound of claim 8 present invention. All documents described herein are incor wherein the metal of the organometallic compound is selected porated by reference herein, including any priority docu from boron, tin, copper, magnesium, zinc, aluminum, lithium ments and/or testing procedures to the extent they are not and Zirconium. US 2010/01 13717 A1 May 6, 2010 97

10. A substituted metallocene compound produced by the 17. The substituted metallocene compound of claim 10 process comprising: whereiny is 1, and Q is a bridging group containing boron or (a) providing a first compound represented by the formula a Group 14, 15 or 16 element. (2): 18. The substituted metallocene compound of claim 10 wherein y is 1 and Q is selected from: P(=S)R', P(=Se)R', P(=O)R', RC, R,Si, R'Ge. RCCR', RCCR'CR', RCCR'CR'CR', RC–CR, RC–CRCR, RCCR'—CRCR', RC–CR'CR'—CR, RC–CRCR'CR, RCSiR', R"SiSiR', RCSiR'CR', R'SiCR'SiR', RC–CR'SiR', RCGeR', R'GeGeR', wherein RCGeR',CR', R'GeCR'GeR', R'SiGeR', M is a group 3, 4, 5 or 6 transition metal atom, or a R'C=CR'GeR', RB, RC BR", RC BR CR', lanthanide metal atom, or actinide metal atom; RC O CR, R'CR'C O CR'CR's RC each of J and E is independently a substituted or unsubsti O CR'CR', RC O CR'—CR', RC S CR', tuted, monocyclic or polycyclic ligand pi-bonded to M, RCR'C S CRCR', R"C S CR'CR', wherein at least one of J and E includes at least one RC S-CR'—CR', RC Se CR', R'CR'C— halogen or sulfonate substituent directly bonded to an Se CRCR, RC Se CRCR's RC Se sp carbonatomata bondable ring position of the ligand; CR'—CR, RC N=CR, RC NR CR, RC Q is an optional bridging group that is bonded to E and J. NR CRCR's RC NR' CR'—CR', RCR'C and is present wheny is one and absent wheny is Zero; NR CRCR's RC P=CR', RC PR CR's O, y is Zero or one; and S, Se, Te, NR", PR', AsR', SbR', O O, S. S. R'N NR', each X is, independently, a univalent anionic ligand, or two RP PR', O S, O NR', O PR', S NR', S PR', X are joined and bound to the metal atom to form a and RN PR' where R' is hydrogen or a C-C contain metallocycle ring, or two X are joined to form a chelat ing hydrocarbyl, substituted hydrocarbyl, halocarbyl, ing ligand, a diene ligand, or an alkylidene ligand; and substituted halocarbyl, silylcarbyl or germylcarbyl sub (b) reacting said first compound with a transfer-agent stituent and optionally two or more adjacent R may join which comprises a hydrocarbyl, substituted hydrocar to form a Substituted or unsubstituted, saturated, par byl, halocarbyl, substituted halocarbyl, silylcarbyl, ger tially unsaturated or aromatic, cyclic or polycyclic Sub mylcarbyl radical capable of replacing said at least one stituent. halogen or Sulfonate Substituent of said first compound 19. The substituted metallocene compound of claim 10 under reaction conditions in the presence of a coupling whereiny is 1 and Q is selected from the group consisting of catalyst. CH, CHCH. SiMe. SiPh. SiMePh, Si(CH), Si(CH), 11. The substituted metallocene compound of claim 10 O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, and wherein at least one of J and E comprises a substituted or PBu, where Me is methyl, Ph is phenyl, Et is ethyl, Pr is unsubstituted monocyclic arenyl ligand or Substituted or propyl, and Bu is butyl. unsubstituted polycyclic arenyl ligand. 20. The substituted metallocene compound of claim 10 12. The substituted metallocene compound of claim 10 wherein the transfer-agent is an organometallic compound. wherein at both J and E comprise a substituted or unsubsti 21. The substituted metallocene compound of claim 20 tuted monocyclic arenyl ligand or polycyclic arenyl ligand. wherein the metal of the organometallic compound is selected 13. The substituted metallocene compound of claim 10 from boron, tin, copper, magnesium, zinc, aluminum, lithium wherein each of J and E is independently a substituted or and Zirconium. unsubstituted cyclopentadienyl ligand, a Substituted or 22. A substituted metallocene compound produced by a unsubstituted heterocyclopentadienyl ligand, a substituted or process comprising: unsubstituted indenyl ligand, a Substituted or unsubstituted (a) providing a first compound represented by the formula heteroindenyl ligand, or a substituted or unsubstituted fluo (3): renyl ligand, a substituted or unsubstituted heterofluorenyl ligand, and a substituted or unsubstituted cyclopentanaph thyl, or a Substituted or unsubstituted heterocyclopentanaph thyl ligand, or a substituted or unsubstituted heterophenyl ligand, or a Substituted or unsubstituted heterocyclopentap entalenyl ligand, or a Substituted or unsubstituted heterocy clopentaindenyl ligand, or a substituted or unsubstituted het erobenzocyclopentaindenyl ligand. 14. The substituted metallocene compound of claim 10 wherein the halogen or Sulfonate Substituent is a chloro, wherein bromo or iodo Substituent. M is a Group 3, 4, 5 or 6 transition metal atom, or a 15. The substituted metallocene compound of claim 10 lanthanide metal atom, or actinide metal atom; wherein the halogen substituent or sulfonate is a chloro or Z is a Substituted or unsubstituted, monocyclic or polycy bromo substituent. clic ligand that is pi-bonded to M: 16. The substituted metallocene compound of claim 10 Q' is an optional bridging group that is bonded to Z and T. whereiny is 1, and Q is a bridging group containing at least and is present wheny is one and absent wheny is Zero; one Group 13, 14, 15, or 16 element. y is Zero or one; and US 2010/01 13717 A1 May 6, 2010 98

T is a heteroatom with a coordination number of three from ethyl, all propyl isomers, all butyl isomers, phenyl, benzyl, Group 15 or with a coordination number of two from phenethyl, 1-adamantyl, cyclododecyl, cyclohexyl and nor Group 16 of the Periodic Table of Elements: bornyl. R" is selected from a C-C substituted or unsubstituted 31. The substituted metallocene compound of claim 22 monocyclic or polycyclic ring structure Substituent that wherein when the halogen or sulfonate substituent is on R", is partially unsaturated, unsaturated or aromatic; or a then R" is selected from the group consisting of 2-bromophe C-Coo substituted or unsubstituted, unsaturated or par nyl, 3-bromophenyl, 4-bromophenyl, 2,6-diisopropyl-4-bro tially unsaturated, linear or branched alicyclic hydrocar mophenyl, 2,6-dimethyl-4-bromophenyl, 2,4,6-trimethyl-3- byl Substituent; or a C-Coo substituted or unsubstituted bromophenyl, 2-bromo-4,6-dimethylphenyl, 2-bromo-4- saturated hydrocarbyl radical; methylphenyl, 2-bromo-3,4,6-trimethylphenyl, 2-bromo-4- t is the coordination number of the heteroatom T (2 or 3) fluorophenyl, 2-bromo-4,6-difluorophenyl, 2,6- where “t-1-y’ indicates the number of R" substituents dibromophenyl, 2,6-dibromo-4-methylphenyl, 2,6-dibromo bonded to T; and 4-fluorophenyl, 2,5-dibromophenyl, and 2,4-dibromophenyl. each X is, independently, a univalent anionic ligand, or two 32. The substituted metallocene compound of claim 22 X are joined and bound to the metal atom to form a whereiny is 1 and Q' is a bridging group containing boron or metallocycle ring, or two X are joined to form a chelat a Group 14, 15 or 16 element. ing ligand, a diene ligand, or an alkylidene ligand; 33. The substituted metallocene compound of claim 22 provided that Z is substituted with at least one halogen or whereiny is 1 and Q' is selected from the group consisting of sulfonate substituent directly bonded to any sp carbon P(=S)R', P(=Se)R', P(=O)R', RC, R'Si, R'Ge. atom at a bondable ring position of the ligand Z, or that RCCR's RCCR'CR's RCCR'CR'CR', R'C—CR', R" is substituted with at least one halogen or sulfonate RC–CR'CR, RCCR'—CRCR, RC—CRCR'—CR', substituent bonded to an sp carbon atom, or both; R'C–CR'CR'CR', RCSiR R'SiSiR, RCSiR'CR', (b) reacting said first compound with a transfer-agent R'SiCR'SiR, R'C—CR'SiR', RCGeR', R'GeGeR', which comprises a hydrocarbyl, substituted hydrocar RC GeR'CR, R'GeCR'GeR', RSiGeR', byl, halocarbyl, substituted halocarbyl, silylcarbyl, ger R'C–CR'GeR', RB, RC BR", RC BR CR', mylcarbyl radical capable of replacing said at least one R'C O CR's RCRC O CRCR, RC O— halogen or Sulfonate Substituent of said first compound CR'CR's RC O CR'—CR', RC S CR', under reaction conditions in the presence of a coupling R'CR'C S CR'CR's RC S CR'CR's RC S catalyst. CR'—CR', RC Se CR', RCRC Se CRCR', RC Se CR'CR', RC Se–CR'—CR', RC 23. The substituted metallocene compound of claim 22 N=CR', RC NR CR's RC NR CR'CR'R'C wherein Z comprises a Substituted or unsubstituted monocy NR' CR'—CR', RCR'C NR CRCR's RC clic arenyl ligand or a Substituted or unsubstituted polycyclic P—CR', and RC PR CR', where R is hydrogen or a arenyl ligand. C-C containing hydrocarbyl, Substituted hydrocarbyl, 24. The substituted metallocene compound of claim 22 halocarbyl, substituted halocarbyl, silylcarbyl or germylcar wherein Z includes one or more ring heteroatoms selected byl substituent and optionally two or more adjacent R may from boron, a Group 14 atom that is not carbon, a Group 15 join to form a Substituted or unsubstituted, Saturated, partially atom, and a Group 16 atom. unsaturated or aromatic, cyclic or polycyclic Substituent. 25. The substituted metallocene compound of claim 22 34. The substituted metallocene compound of claim 22 wherein Z is independently a substituted or unsubstituted whereiny is 1 and Q' is selected from the group consisting of cyclopentadienyl ligand, a Substituted or unsubstituted het CH, CHCH, SiMe. SiPh. SiMePh, Si(CH), and erocyclopentadienyl ligand, a Substituted or unsubstituted Si(CH), where Me is methyl, and Ph is phenyl. indenyl ligand, a Substituted or unsubstituted heteroindenyl 35. The substituted metallocene compound of claim 22 ligand, or a substituted or unsubstituted fluorenyl ligand, a wherein said transfer-agent is an organometallic compound. substituted or unsubstituted heterofluorenyl ligand, and a sub 36. The substituted metallocene compound of claim 35 stituted or unsubstituted cyclopentanaphthyl, or a Substituted wherein the metal of the organometallic compound is selected or unsubstituted heterocyclopentanaphthyl ligand, or a Sub from boron, tin, copper, magnesium, zinc, aluminum, lithium stituted or unsubstituted heterophenyl ligand, or a substituted and Zirconium. or unsubstituted heterocyclopentapentalenyl ligand, or a Sub 37. A catalyst system comprising the Substituted metal stituted or unsubstituted heterocyclopentaindenyl ligand, or a locene compound of claim 1 and an activator. substituted or unsubstituted heterobenzocyclopentaindenyl 38. The catalyst system of claim 37 wherein the activator is ligand. selected from the group consisting of alumoxane and ionic 26. The substituted metallocene compound of claim 22 activators. wherein the halogen or Sulfonate Substituent is a chloro, 39. A process for polymerizing olefins comprising contact bromo or iodo Substituent. ing the catalyst system of claim 37 with at least one olefin. 27. The substituted metallocene compound of claim 22 40. The process of claim 39 wherein said at least one olefin wherein the halogen substituent is a chloro or bromo substitu comprises ethylene and/or propylene. ent. 41. A catalyst system comprising the Substituted metal 28. The substituted metallocene compound of claim 22 locene compound of claim 10 and an activator. whereint-1-y is equal to 1. 42. The catalyst system of claim 41 wherein the activator is 29. The substituted metallocene compound of claim 22 selected from the group consisting of alumoxane and ionic wherein T is nitrogen. activators. 30. The substituted metallocene compound of claim 22 43. A process for polymerizing olefins comprising contact wherein R" is selected from the group consisting of methyl, ing the catalyst system of claim 41 with at least one olefin. US 2010/01 13717 A1 May 6, 2010 99

44. The process of claim 43 wherein said at least one olefin (m-2-methyl-4-(3-trifluoromethylphenyl)indenyl)(m- comprises ethylene and/or propylene. pentamethylcyclopentadienyl)hafnium dichloride, 45. A catalyst system comprising the Substituted metal (m-2-methyl-4-(2-methoxyphenyl)indenyl)(m-pentam locene compound of claim 22 and an activator. ethylcyclopentadienyl)hafnium dichloride, 46. The catalyst system of claim 45 wherein the activator is (m-2-methyl-4-(4-biphenyl)bromoindenyl)(m-pentam selected from the group consisting of alumoxane and ionic ethylcyclopentadienyl)hafnium dichloride, activators. (m-2-methyl-4-(1-naphthyl)indenyl)(m-pentamethylcy 47. A process for polymerizing olefins comprising contact clopentadienyl)hafnium dichloride, ing the catalyst system of claim 45 with at least one olefin. (m-2-methyl-4-(2-thienyl)indenyl)(m-pentamethylcy 48. The process of claim 47 wherein said at least one olefin clopentadienyl)hafnium dichloride, comprises ethylene and/or propylene. (m-2-methyl-4-(2-benzothienyl)indenyl)(m-pentameth 49. The compound of claim 1, wherein the compound is ylcyclopentadienyl)hafnium dichloride, selected from the group consisting of: (m-2-methyl-4-(2-furyl)indenyl)(m-pentamethylcyclo (m-2,4-dimethylindenyl)(m-pentamethylcyclopentadi pentadienyl)hafnium dichloride, enyl)Zirconium dichloride, (m-2-methyl-4-(2-benzofuryl)indenyl)(m-pentamethyl (m-2-methyl-4-phenylindenyl)(m-pentamethylcyclopen cyclopentadienyl)hafnium dichloride, tadienyl)Zirconium dichloride, (m-2-methyl-4-styrylindenyl)(m-pentamethylcyclopen (m-2-methyl-4-(p-tolyl)indenyl)(m-pentamethylcyclo tadienyl)hafnium dichloride (cis and trans), pentadienyl)Zirconium dichloride, (m-2-methyl-4-(4-fluoro styryl)indenyl)(m-pentamethyl (m-2-methyl-4-(m-tolyl)indenyl)(m-pentamethylcyclo cyclopentadienyl)hafnium dichloride (trans), and pentadienyl)Zirconium dichloride, (m-2-methyl-4-(1,2-butoxyvinyl)indenyl)(m-pentameth (m-2-methyl-4-(o-tolyl)indenyl)(m-pentamethylcyclo ylcyclopentadienyl)hafnium dichloride. pentadienyl)Zirconium dichloride, 50. The compound of claim 1, wherein the compound is (m-2-methyl-4-(4-t-butylphenyl)indenyl)(m-pentameth selected from the group consisting of: ylcyclopentadienyl)Zirconium dichloride, (m-2,4-dimethylindenyl)(m-pentamethylcyclopentadi (m-2-methyl-4-(4-fluorophenyl)indenyl)(m-pentameth enyl)hafnium dichloride, ylcyclopentadienyl)Zirconium dichloride, (m-2-methyl-4-(p-tolyl)indenyl)(m-pentamethylcyclo (m-2-methyl-4-(3-trifluoromethylphenyl)indenyl)(m- pentadienyl)hafnium dichloride, pentamethylcyclopentadienyl)Zirconium dichloride, (m-2-methyl-4-(m-tolyl)indenyl)(m-pentamethylcyclo (m-2-methyl-4-(2-methoxyphenyl)indenyl)(m-pentam pentadienyl)hafnium dichloride, ethylcyclopentadienyl)Zirconium dichloride, (m-2-methyl-4-(4-t-butylphenyl)indenyl)(m-pentameth (m-2-methyl-4-(4-biphenyl)bromoindenyl)(m-pentam ylcyclopentadienyl)hafnium dichloride, and ethylcyclopentadienyl)Zirconium dichloride, (m-2-methyl-4-(1-naphthyl)indenyl)(m-pentamethylcy (m-2-methyl-4-phenylindenyl)(m-pentamethylcyclopen clopentadienyl)Zirconium dichloride, tadienyl)hafnium dichloride. (m-2-methyl-4-(2-thienyl)indenyl)(m-pentamethylcy 51. The compound of claim 1, wherein the compound is clopentadienyl)Zirconium dichloride, selected from the group consisting of: (m-2-methyl-4-(2-benzothienyl)indenyl)(m-pentameth (m-4,7-di-(3-trifluoromethylphenyl)inden-1-yl)(m-pen ylcyclopentadienyl)Zirconium dichloride, tamethylcyclopentadienyl)Zirconium dichloride (m-2-methyl-4-(2-furyl)indenyl)(m-pentamethylcyclo (m-4-(4-dimethylaminophenyl)-6-chloroindenyl)(m- pentadienyl)Zirconium dichloride, pentamethylcyclopentadienyl)Zirconium dichloride, (m-2-methyl-4-(2-benzofuryl)indenyl)(m-pentamethyl (m-4,7-di-(3-trifluoromethylphenyl)inden-1-yl)(m-pen cyclopentadienyl)Zirconium dichloride, tamethylcyclopentadienyl)hafnium dichloride, and (m-2-methyl-4-styrylindenyl)(m-pentamethylcyclopen (m-4-(4-dimethylaminophenyl)-6-chloroindenyl)(m- tadienyl)Zirconium dichloride (cis and trans), pentamethylcyclopentadienyl)hafnium dichloride. (m-2-methyl-4-(4-fluorostyryl)indenyl)(m-pentamethyl 52. The compound of claim 1, wherein the compound is cyclopentadienyl)Zirconium dichloride (trans), selected from the group consisting of: (m-2-methyl-4-(1,2-butoxyvinyl)indenyl)(m-pentameth (m-2,4-dimethylindenyl)(m-cyclopentadienyl)zirconium ylcyclopentadienyl)Zirconium dichloride, dichloride, (m-2,4-dimethylindenyl)(m-pentamethylcyclopentadi (m-2-methyl-4-phenylindenyl)(m-cyclopentadienyl)Zir enyl)hafnium dichloride, conium dichloride, (m-2-methyl-4-phenylindenyl)(m-pentamethylcyclopen (m-2-methyl-4-(p-tolyl)indenyl)(m-cyclopentadienyl) tadienyl)hafnium dichloride, Zirconium dichloride, (m-2-methyl-4-(p-tolyl)indenyl)(m-pentamethylcyclo (m-2-methyl-4-(m-tolyl)indenyl)(m-cyclopentadienyl) pentadienyl)hafnium dichloride, Zirconium dichloride, (m-2-methyl-4-(m-tolyl)indenyl)(m-pentamethylcyclo (m-2,4-dimethylindenyl)(m-cyclopentadienyl)hafnium pentadienyl)hafnium dichloride, dichloride, (m-2-methyl-4-(o-tolyl)indenyl)(m-pentamethylcyclo (m-2-methyl-4-phenylindenyl)(m-cyclopentadienyl) pentadienyl)hafnium dichloride, hafnium dichloride, (m-2-methyl-4-(4-t-butylphenyl)indenyl)(m-pentameth (m-2-methyl-4-(p-tolyl)indenyl)(m-cyclopentadienyl) ylcyclopentadienyl)hafnium dichloride, hafnium dichloride, and (m-2-methyl-4-(4-fluorophenyl)indenyl)(m-pentameth (m-2-methyl-4-(m-tolyl)indenyl)(m-cyclopentadienyl) ylcyclopentadienyl)hafnium dichloride, hafnium dichloride.