US007 271121B2

(12) United States Patent (10) Patent No.: US 7,271,121 B2 Small et al. (45) Date of Patent: Sep. 18, 2007

(54) DIIMINE METAL COMPLEXES, METHODS WO WOOO,5832O 10, 2000 OF SYNTHESIS, AND METHODS OF USING WO WOOOf 66638 11 2000 N OLGOMERIZATION AND WO WOOOf 6828O 11 2000 POLYMERIZATION WO WO O1? 10875 A1 2, 2001 WO WO O1, 58.874 A1 8, 2001 (75) Inventors: Brooke L. Small, Kingwood, TX (US); WO WO O1.7483.0 A1 10, 2001 Michael Carney, Eau Claire, WI (US) WO WO O2/OO339 A2 1, 2002 WO WO O2,28805 A2 4/2002 (73) Assignee: Chevron Phillips Chemical Company WO WO O2,34701 A1 5, 2002 WO WO O2,34746 A2 5, 2002 LP, The Woodlands, TX (US) WO WO O2/O90365 A1 11, 2002 WO WO O2/096919 A1 12/2002 (*) Notice: Subject to any disclaimer, the term of this WO WO O3,O10207 A1 2, 2003 patent is extended or adjusted under 35 WO WO O3,O11876 A1 2, 2003 U.S.C. 154(b) by 0 days. WO WO 03/022889 A1 3, 2003 WO WO O3,053890 A1 T 2003 (21) Appl. No.: 11/186,039 WO WO O3,053,891 A1 T 2003 WO WO 2004/O26795 A2 4/2004 (22) Filed: Jul. 21, 2005 WO WO 2004/O29012 A1 4/2004 (65) Prior Publication Data WO WO 2004/033398 A1 4/2004 WO WO 2004/056477 A1 T 2004 US 2007/0021608 A1 Jan. 25, 2007 WO WO 2004/056478 A1 T 2004 WO WO 2004/056479 A1 T 2004 (51) Int. Cl. WO WO 2004/056480 A1 T 2004 BOI 3/8 (2006.01) CSF 4/80 (2006.01) C07F 15/02 (2006.01) OTHER PUBLICATIONS (52) U.S. Cl...... 502/167; 526/161; 556/23 Wang et al. “Catalytic Sulfoxidation and Epoxidation with a Mn(III) (58) Field of Classification Search ...... 526/161; Triazacorrole: Evidence for A “Third Oxidant” in High-Valent 502/167: 556/23 Porphyrinoid Oxidations” Journal of the American Chemical Soci See application file for complete search history. ety 2004, vol. 126, pp. 18-19.* Small et al. “Highly Active Iron and Cobalt Catalysts for the (56) References Cited Polymerization of Ethylene' Journal of the American Chemical Society 1998, vol. 120, pp. 4049-4050.* U.S. PATENT DOCUMENTS DuBois, Thomas D. "Four- and Five-Coordinate Nickel(II) Com plexes of 2,3-Butanedionebis(2-diphenylphosphinoethylamine)” 4,971,986 A 11/1990 Stanek et al. Inorganic Chemistry 1972, vol. 11, pp. 718-722.* 5,811,618 A 9, 1998 Wu 5,880,241 A 3, 1999 Brookhart et al. Chang et al. “Model Complexes of the Active Site in Peptide 5,955,555 A 9, 1999 Bennett Deformylase: A New Family of Mononuclear N2S-M(II) Com 6,103,946 A 8/2000 Brookhart, III et al. plexes” Inorganic Chemistry 2001, vol. 40, pp. 194-195.* 6,184,428 B1 2, 2001 Zahoor et al. Nelson, S. Martin, et al., “Metal-ion Controlled Reactions of 6,214,761 B1 4/2001 Bennett 2,6-Diacetylpyridine with 1,2-Di-aminoethane and 2,6- 6,281,303 B1 8, 2001 Lavoie et al. Diformylpyridine wit o-Phenylenediamine and the Crystal and 6,489,497 B1 12/2002 Brookhart, III et al. Molecular Structure of a Pentagonal Pyramidal Cadmium (II) 6,545,108 B1 * 4/2003 Moody et al...... 526, 161 Complex containing Unidentate o-Phenylenediamine.” 1982, pp. 6,683,141 B1 1/2004 Gibson et al. 407-415. 6,720,468 B2 4/2004 Elomari et al. 6,818,715 B1 1 1/2004 Kristen et al. (Continued) 6.825,297 B1 1 1/2004 Devore et al. Primary Examiner Kamal A. Saeed 6,894,134 B2 5, 2005 Brookhart et al. 2002fOO16425 A1 2/2002 De Boer et al. Assistant Examiner Joseph R. Kosack 2002/0028941 A1 3, 2002 De Boer et al. (74) Attorney, Agent, or Firm—Conley Rose, P.C.; Rodney 2002fOO61987 A1 5/2002 Lenges B. Carroll; K. KaRan Reed 2003.00366.15 A1 2/2003 Brookhart, III et al. 2003/0050494 A1 3/2003 Brookhart, III et al. (57) ABSTRACT 2003.01.19921 A1 6, 2003 De Boer et al. 2004.0068154 A1 4/2004 Small Methods for making C-diimine metal complexes are 2004/O180778 A1 9, 2004 Small described. The methods comprise forming an O-diimine FOREIGN PATENT DOCUMENTS metal complex imine bond in the presence of a metal salt or an O-acylimine metal complex. The method is particularly CN 1306014 8, 2001 using for the production of C-diimine metal complexes CN 1374281 10, 2002 DE 198 12 066 A1 1, 1999 having two different C.-diimine nitrogen groups. The C-di EP 1 325 924 A1 T 2003 imine metal complexes are useful for polymerizing or oli JP 20O2371062 12/2002 gomerizing olefins. JP 2003147009 5, 2003 WO WO96,111.93 4f1996 16 Claims, 2 Drawing Sheets US 7,271,121 B2 Page 2

OTHER PUBLICATIONS Esteruelas, Miguel A., et al., “Preparation, Structure, and Ethylene Polymerization Behavior of Bis (imino) pyridyl Chromium(III) Britovsek, George J.P. et al., “Novel olefin polymerization catalysts Complexes.” Organometallics—American Chemical Society, Jan. based on iron and cobalt.” Chem Comm, 1998, pp. 849-850. 1, 2003, pp. 395-406, vol. 22. Small, Brooke L., et al., “New Iron and Cobalt Catalysts for the McGuinness, David S., et al., “Novel Cr-PNP complexes as cata Polymerization of Olefins.” Dallas ACS, Mar. 1998, p. 213, vol. 39. lysts for the trimerisation of ethylene.” ChemComm, Jan. 2, 2003, Small, Brooke L., et al., “Highly Active Iron and Cobalt Catalysts pp. 334-335. for the Polymerization of Ethylene.” American Chemical Society, Chen, Yaofeng, et al., “Fluoro-Substituted 2,6-Bis(imino)pyridyl Apr. 14, 1998, pp. 4049-4050, vol. 120. Iron and Cobalt Complexes: High-Activity Ethylene Oligomeriza Small, Brooke L., et al., “Iron-Based Catalysts with Exceptionally tion Catalysts.” Organometallics—American Chemical Society, High Activities and Selectivities for Oligomerization of Ethylene to Feb. 15, 2003, pp. 1231-1236, vol. 22. Linear a-Olefins,” American Chemical Society, Jul. 7, 1998, pp. 7143-7144, vol. 120. McGuinness, David S., et al., “First Cr(III)-SNS Complexes and Kumar, R.N., et al., “Mononuclear and Binuclear Complexes of Their Use as Highly Efficient Catalysts for the Trimerization of Fe(II) and Cu(II) with 2,6-Diacetyl Pyridine Monoxime and Ethylene to 1-Hexene,” JACS Communications—American Phenylene Diamine.” Asian Journal of Chemistry, Jul.-Sep. 1999, Chemical Society, Apr. 15, 2003, pp. 5272-5273. pp. 964-969, vol. 11, No. 3. Small, Brooke L., et al., “Comparative Dimerization of 1-Butene Bennett, Alison M. A., “Novel, highly active iron and cobalt with a Variety of Metal Catalysts, and the Investigation of a New catalysts for olefin polymerization,” Enabling Science-American Catalyst for C-H Bond Activation.” Full Paper Chem. Eur, J., Chemical Society, Chemtech, Jul. 1999, pp. 24-28, vol. 29, No. 7. 2004, pp. 1014-1020 & Supporting Information (2 pgs.), vol. 10. Britovsek, George J.P. et al., “Iron and Cobalt Ethylene Polymer Small, Brooke L., et al., “New Chromium Complexes for Ethylene ization Catalysts Bearing 2,6-Bis(imino) Pyridyl Ligands: Synthe Oligomerization: Extended Use of Tridentate Ligands in Metal sis, Structures, and Polymerization Studies.” American Chemical Catalyzed Olefin Polymerization.” Macromolecules—American Society, Sep. 11, 1999, pp. 8728-8740, vol. 121. Chemical Society, May 18, 2004, pp. 4375-4386, vol. 37. Britovsek, George J.P. et al., “Oligomerisation of Ethylene by Rosenberger, Volker, et al.; “Diazadien-Komplexe des Rutheniums, Bis(imino)pyridyliron and—cobalt Complexes.” Full XIII, Bis(diazadien) ruthenium: Isomerisierung, Hydrierung, Paper Chem. Eur, J., 2000, pp. 2221-2231, vol. 6, No. 12. Metaillierung; Struktur eines Kalium(tmeda)2-ruthenats(0).” Jour Katritzky, Alan R., et al., “Syntheses of 1,4-Benzothiazepines and nal of Organometallic Chemistry, vol. 411, Elsevier Sequoia, 1991, 1,4-Benzoxazepines via Cyclizations of 1-2-Arylthio(oxy)ethyl pp. 445-456. 5-benzotriazolyl-2-pyrrolidinones and 3-Benzotriazolyl-2-2- Tempel, Daniel J., et al.; “Mechanistic Studies of Pd(II)-a-Diimine arylthio(Oxy)ethyl-1-isoindolinones,” J.Org, Chem.—American Catalyzed Olefin Polymerizations,” J. Am. Chem. Soc., vol. 122, Chemical Society, Jul. 18, 2001, pp. 5590-5594, vol. 66. American Chemical Society, 2000, pp. 6686-6700. Small, Brooke L., et al., “Iron Catalysts for the Head-to-Head Stojcevic, Goran, et al., "Coordination insertion reactions of Dimerization of a-Olefins and Mechanistic Implications for the acrylonitrile into Pd-H and Pd-methyl bonds in a dimine-pal Production of Linear a-Olefins.” Organometallics—American ladium(II) system.” Journal of Organometallic Chemistry, vol. 690, Chemical Society, Nov. 22, 2001, pp. 5738-5744, vol. 20. Elsevier, 2005, pp. 4349-4355. Carter, Anthea, et al., "High activity ethylene trimerisation catalysts Invitation to Pay Additional Fees and Partial Search Report of based on diphosphine ligands,” Chem.Commun.-The Royal Society PCT/US2006/028068, Jan. 5, 2007, 6 pgs. of Chemistry, Mar. 20, 2002, pp. 858-859 & Supplementary Infor mation (2 pgs.). * cited by examiner U.S. Patent Sep. 18, 2007 Sheet 1 of 2 US 7,271,121 B2

Figure 1 - ORTEP Diagram of the X-Ray Crystal Structure for the o-E)iimine Metal Complex Produced in Example 5

U.S. Patent Sep. 18, 2007 Sheet 2 of 2 US 7,271,121 B2

Figure 2 - ORTEP Diagram of the X-Ray Crystal Structure for the a-Diimine Metal Complex Produced in Example 7

CI(5A)

O C S(1A)

US 7,271,121 B2 1. 2 DIIMINE METAL COMPLEXES, METHODS group and a linking group linking the metal salt complexing OF SYNTHESIS, AND METHODS OF USING group to the -NH group. In another embodiment, the N OLGOMERIZATION AND C-acylimine compound comprises an O-acylimine group POLYMERIZATION and an O-acylimine nitrogen group comprising a metal salt complexing group and a linking group linking the metal salt CROSS-REFERENCE TO RELATED complexing group to the C-acylimine nitrogen atom, and the APPLICATIONS primary amine consists of an —NH group and an organyl group consisting of an inert functional group or a hydrocar The present application is related to U.S. patent applica byl group. In yet another embodiment, the method for tion Ser. No. 11/186.306 and U.S. patent application Ser. No. 10 producing an O-diimine metal complex comprises: a) con 11/186,038 (now U.S. Pat. No. 7,129,304 issued Oct. 31, tacting an O-acylimine metal complex and a primary amine; 2006), each having like title and filed on Jul. 21, 2005. and b) recovering the C-diimine metal complex. FIELD OF THE INVENTION In another aspect, the present invention provides for an 15 C-diimine metal complex composition comprising a metal The present application relates generally to olefin oligo salt complexed to a bidentate or tridentate C-diimine com merization. More particularly, the present application relates pound wherein the C-diimine compound comprises an O-di to C-diimine metal complexes, methods of producing C-di imine group, a first imine nitrogen group, and a secondimine imine metal complexes, and the use of C-diimine metal nitrogen group which is different from the first imine nitro complexes in the oligomerization and/or polymerization of gen group. In embodiments, the C-diimine compound is olefins. tridentate, the C-diimine group is derived from an O-diacyl compound, the first imine nitrogen group consists of a C to BACKGROUND OF THE INVENTION Co organyl group consisting of inert functional groups or a C to Cohydrocarbyl group, and the second imine nitrogen Olefins, also commonly known as alkenes, are important 25 group comprises a metal salt complexing group and a items of commerce. Their many applications include linking group linking the metal salt complexing group to the employment as intermediates in the manufacture of deter imine nitrogen group. In another embodiment, the C-diimine gents, as more environmentally friendly replacements where compound is bidentate, the C-diimine group is derived from refined oils might otherwise be used, as monomers, and as an C-diacyl compound, the first imine nitrogen group con intermediates for many other types of products. An impor 30 sists of a C to Co organyl group consisting of inert tant Subset of olefins are olefin oligomers, and one method functional groups or a C to Co. hydrocarbyl group, and the of making olefin oligomers is via oligomerization of ethyl Second imine nitrogen group consists of a C to Co organyl ene, which is a catalytic reaction involving various types of group consisting of inert functional groups or a C to Co catalysts. Examples of catalysts used commercially in poly hydrocarbyl group. In further embodiments, the C-diimine merization and oligomerization of olefins include alkylalu 35 metal complex comprises a metal salt comprising iron minum compounds, certain nickel-phosphine complexes, complexed to a tridentate C-diimine compound comprising: and a titanium halide with a Lewis acid, such as diethyl 1) an O-diimine group derived from acenaphthenequinone, aluminum chloride. phenanthrenequinone, or pyrenequinone; 2) a first imine Another group of olefin polymerization catalysts is nitrogen group consisting of a 2,6-dimethylphenyl group, a derived from pyridine bis-imines. With catalysts of this type, 40 2,6-diethylphenyl group, a 2,6-diisopropylphenyl group, or a nitrogen-based ligand engages in a coordination reaction a 2,6-di-tert-butylphenyl group; and 3) a second imine with a transition metal salt. The coordination reaction forms nitrogen group comprising a metal salt complexing group a metal complex, which is a catalyst precursor. The metal and a linking group linking the metal salt complexing group complex further reacts with another precursor or activator to to the second imine nitrogen atom. generate a metal alkyl or metal hydride species. The catalyst 45 In yet another aspect, the present invention provides a resulting from the generation of the metal alkyl or metal process for producing alpha olefins comprising: a) contact hydride species polymerizes olefins. ing ethylene, an O-diimine metal complex, and a cocatalyst; Applications and demand for olefin polymers and oligo and forming an oligomerized ethylene product comprising mers continue to multiply, and competition to Supply them alpha olefins. In embodiments, the C-diimine metal complex correspondingly intensifies. Thus, additional novel and 50 comprises a metal salt complexed to an O-diimine com improved catalysts and methods for olefin polymerization pound, wherein the C-diimine compound comprises: 1) an and oligomerization are desirable. C-diimine group derived from an O-diacyl compound; 2) a first imine nitrogen group consisting of a C to Co organyl SUMMARY OF THE INVENTION group consisting of inert functional groups or a C to Co 55 hydrocarbyl group; and 3) a second imine nitrogen group In an aspect the present invention provides a method for comprising a metal salt complexing group and a linking producing an O-diimine metal complex comprising forming group linking the metal salt complexing group to the imine at least one imine bond in the presence of a metal salt, metal nitrogen group. In other embodiments, the C-diimine metal complex, or combinations thereof. In embodiments, the complex comprises a metal salt comprising iron complexed method for producing an O-diimine metal complex com 60 to an O-diimine compound comprising: 1) an O-diimine prises: a) contacting an O-acylimine compound, a metal salt, group derived from acenaphthenequinone, phenanthrene and a primary amine; and b) recovering the C-diimine metal quinone, or pyrenequinone; 2) a first imine nitrogen group complex. In some embodiments, the O-acylimine compound consisting of a 2,6-dimethylphenyl group, a 2,6-diethylphe comprises an O-acylimine group and an O-acylimine nitro nyl group, or a 2,6-diisopropylphenyl group; and 3) a second gen group consisting of an organyl group consisting of inert 65 imine nitrogen group comprising a metal salt complexing functional groups or a hydrocarbyl group and the primary group and a linking group linking the metal salt complexing amine comprises an —NH group, a metal salt complexing group to the second imine nitrogen atom. US 7,271,121 B2 3 4 DESCRIPTION OF THE DRAWINGS C-acylimine group (an O-acylimine nitrogen group). For the purpose of this application the —C=N portion of a FIG. 1 represents the ORTEP diagram of the X-ray crystal pyridine ring, or pyridine containing ring system (shown in structure for the C-diimine metal complex produced in its localized or delocalized form) does not constitute an Example 5. imine group. FIG. 2 represents the ORTEP diagram of the X-ray crystal For purposes of this application, a “hydrocarbyl group' structure for the C-diimine metal complex produced in has the definition specified by IUPAC: a univalent group Example 7. formed by removing a hydrogen atom from a hydrocarbon (i.e. a group containing only carbon and hydrogen). A DETAILED DESCRIPTION OF EMBODIMENTS 10 hydrocarbyl group can include the term “alkyl or “alkyl group. A hydrocarbyl group can include rings, ring sys The present application discloses C.-diimine metal com tems, aromatic rings, and aromatic ring systems which plexes, methods for producing C-diimine metal complexes, contain only carbon and hydrogen. and the use of C-diimine metal complexes in the oligomer For purposes of this application, an “organyl group” has ization and/or polymerization of olefins. 15 the definition specified by IUPAC: an organic substituent group, regardless of functional type, having one free Valence Definitions at a carbon atom. Thus, an organyl group can contain organic For the purpose of this application the designation “C.- functional groups and/or atoms other than carbon and hydro represents a relational designation that when preceding a gen (i.e. an organic group that can comprise functional chemical name, either general or specific, indicates that the groups and/or atoms in addition to carbon and hydrogen). two functional groups are on adjacent carbon atoms. Non For example, non-limiting examples of atoms other than limiting examples using the relational O-designation carbon and hydrogen include halogens, oxygen, nitrogen, include, C-dione where the two ketone oxygen atoms are and phosphorus, among others. Non-limiting examples of bonded to adjacent carbon atoms, O-diimine where the two functional groups include ethers, aldehydes, ketones, alde imine nitrogen atoms are bonded to adjacent carbon atoms, 25 hydes, esters, Sulfides, amines, and phosphines, among and O-acylimine where the acyl group oxygen atom and the others. Included in the organyl group definition are heteroa imine nitrogen atom are bonded to adjacent carbon atoms. tom containing rings, heteroatom containing ring systems, The C-relational designation may also be used to describe heteroaromatic rings, and heteroaromatic ring systems. other compounds described herein. Finally, it should be noted that the organyl group definition For purposes of this application, an 'acyl group' is 30 includes the organyl group consisting of inert functional represented by the structure groups, and the hydrocarbyl group as a members. For the purposes of this application, the term or variations of the term “organyl group consisting of inert functional groups' refers to an organyl group wherein the organic 35 functional groups and/or atoms other than carbon and hydro gen present in the functional group are restricted to those functional group and/or atoms other than carbon and hydro gen which do not complex with a metal salt and/or are inert wherein the undesignated Valences may be hydrogen, an under the process conditions defined herein. Thus, the term organyl group, a hydrocarbyl group, and/or any other group 40 or variation of the term “organyl groups consisting of inert as indicated herein. Thus, the term acyl group may include functional groups' further defines the particular organyl ketones and/or aldehydes. The present application may also groups that can be present within the organyl group con refer to Substituent(s)/group(s)/atom(s) attached to the acyl sisting of inert functional groups. Additionally, the term group carbon atom (an acyl carbon group). "organyl group consisting of inert functional groups' can For the purpose of this application, the term “imine 45 refer to the presence of one or more inert functional groups group' is represented by the structure within the organyl group. The term or variation of the "organyl group consisting of inert functional group' defini tion includes the hydrocarbyl group as a member. For purposes of this application, an “inert functional 50 group' is a group which does not substantially interfere with any process described herein in which it takes part and/or does not complex with the metal salt of an O-diimine metal complex. The term “does not complex with the metal salt wherein the undesignated Valences can be hydrogen, an can include groups that could complex with a metal salt but organyl group, a hydrocarbyl group, and/or any other group 55 in particular molecules described herein can not complex as indicated herein. The term imine group comprises both with a metal salt due to its positional relationship within a aldimines and ketimines. The present application may also complexing C-diimine group. For example, while an ether refer to Substituent(s)/group(s)/atom(s) attached to the imine group can complex with a metal salt, an ether group located carbon atom (an imine carbon group) and/or substituent(s)/ at a para position of a Substituted phenyl imine nitrogen group(s)/atom(s) attached to the imine nitrogen atom (an 60 group is an inert functional group because a single metal salt imine nitrogen group). Additionally, the present application molecule can not complex with both the ether group and the may refer to Substituents/groupS/atoms attached to the acyl imine group of the C-diimine compound within the same carbon atom of the O-acylimine group (an O-acylimine acyl molecule. Thus, the inertness of a particular functional carbon group), Substituents/groups/atoms attached to the group is not only related to its functional group's inherent imine carbon atom of the C-acylimine group (an 65 inability to complex the metal salt but can also be related to C-acylimine imine carbon group), and/or substituent(s)/ the functional group's position within the metal complex. group(s)/atom(s) attached to the imine nitrogen atom of the Non-limiting examples of inert functional groups which due US 7,271,121 B2 5 6 not substantially interfere with any process described herein C-acylimine metal complexes, and metal salts are indepen can include halo (fluoro, chloro, bromo and iodo), ethers dent elements within the C-diimine metal complex synthesis (alkoxy group or etheryl group), Sulfides (sulfidyl group), and further described herein. and/or hydrocarbyl groups. The terms “polymerized product having X carbon atoms” C-Diacyl Compounds and "oligomerized product having X carbon atoms.” Generally, C.-diacyl compounds utilized in the production wherein X can be any integer, refers to materials produced of the C-diimine metal complexes comprise two acyl groups in a reactor by monomer polymerization or monomer oli capable of forming an imine group when contacted with a gomerization that has X carbon atoms. Thus, the term primary amine. Appropriate C-diacyl compounds can be polymerized product having X carbon atoms and oligomer 10 those capable of reacting with two primary amines to form ized product having X carbon atoms excludes materials in an C-diimine compound. Within in this specification, the the reactor effluent having X carbon atoms which were not term “capable of reacting with two primary amines to form polymerized or oligomerized (e.g. solvent). an C-diimine compound should not be construed to mean For purposes of this application, a primary carbon group that two primary amines are necessarily added in the same is —CH. 15 step. Nor should the term be construed to mean that an For purposes of this application, a secondary carbon C-diimine compound is necessarily formed as an interme group includes a group of the formula —CH2—, wherein the diate to an O-diimine metal complex. Further, defining an one free Valence (-) is to an atom other than a hydrogen C-diacyl compound as one capable of forming an imine atom (the bond represented by the dash, —, is to atom and/or group when contacted with a primary amine is not neces group to which the secondary carbon group is attached). sarily indicative of methods of forming an imine group. The Thus, the free Valence can be bonded to a halogen atom, term “capable of reacting with two primary amines to form carbon atom, oxygen atom, Sulfur atom, etc. In other words, an C-diimine compound is intended to describe to one the free Valence can be to an organyl group, an organyl skilled in the art the particular C-diacyl compounds which group consisting of inert functional groups, a hydrocarbyl can be utilized in the synthesis of the C-diimine metal group, a functional group, or an inert functional group. 25 complexes described herein. The C-diimine metal com Non-limiting examples of secondary carbon groups include plexes can be produced utilizing any method as described —CH-CH(CH), —CHCl, —CH2CHs. and herein. —CHOCH. One class of C-diacyl compounds that can be used in For purposes of this application, a tertiary carbon group preparing C-diimine metal complexes is an O-ketoaldehyde, includes a group of the formula —CH=, wherein the two 30 which is a compound wherein a ketone oxygen atom and an free Valences (=) are to atoms other than a hydrogen atom aldehyde oxygen atom are bonded to adjacent carbon atoms. (the bond represented by the dash, —, is to atom and/or The O.-ketoaldehydes utilized in the production of the C-di group to which the tertiary carbon group is attached). Thus, imine metal complexes can be any C.-ketoaldehyde capable the two free valences can be independently bonded to a of reacting with two primary amines to form an O-diimine halogen atom, carbon atom, oxygen atom, Sulfur atom, etc. 35 compound. The O-ketoaldehyde can be saturated, unsatur In other words, each of the two free valences can be to an ated, linear, branched, acyclic, cyclic, aromatic, and/or het organyl group, an organyl group consisting of inert func eroaromatic. tional groups, a hydrocarbyl group, a functional group, or an Generally, the C.-ketoaldehyde will have the structure inert functional group. Non-limiting examples of secondary R* C(=O)C(=O)H wherein R* can be an organyl carbon groups include —CH(CH), —CHCl2, —CH 40 group, an organyl group consisting of inert functional (C6H5)2. -cyclohexyl, —CH(CH)OCH, and groups, or a hydrocarbyl group. In some embodiments, R“ CH=CHCH is an organyl group; alternatively, an organyl group consist For purposes of this application, a quaternary carbon ing of inert functional groups; or alternatively, a hydrocarbyl group includes a group of the formula —C=, wherein the group. Generally, R“ can be a C, to Cao organyl group; three free Valences, E, are to atoms other than a hydrogen 45 alternatively, a C to Co organyl group consisting of inert atom (the bond represented by the dash, —, is to atom and/or functional groups; alternatively, a C to Co. hydrocarbyl group to which the quaternary carbon group is attached). group; alternatively, a C to Co organyl group; alternatively, Thus, each of the three free valences can be independently a C to Co organyl group consisting of inert functional bonded to a halogenatom, carbon atom, oxygen atom, Sulfur groups; alternatively, a C to Co. hydrocarbyl group; alter atom, etc. In other words, each of the three free valences can 50 natively, a C to Co organyl group; alternatively, a C to Co be to an organyl group, an organyl group consisting of inert organyl group consisting of inert functional groups; alter functional groups, a hydrocarbyl group, a functional group, natively, a C to Co. hydrocarbyl group; alternatively, a C or an inert functional group. Non-limiting examples of to Cs organyl group; alternatively, a C to Cs organyl group tertiary carbon groups include: —C(CH), —C(CHs), consisting of inert functional groups; or alternatively, a C to 55 Cs hydrocarbyl group. Generally the organyl group, organyl —CC1, C(CH)OCH, -C=CH, -C(CH)CH=CH, group consisting of inert functional groups, or hydrocarbyl —CHs. -CF, and -1-adamanty1. group of the C-ketoaldehyde can be saturated, unsaturated, C.-Diimine Metal Complex, Starting Materials, and Interme acyclic, cyclic, linear, branched, and/or aromatic. diates In some embodiments, R“ represents an acyclic organyl Generally, the C-diimine metal complexes can be pre 60 group, an acyclic organyl group consisting of inert func pared from C-diacyl compounds, two primary amines, and a tional groups, or an acyclic hydrocarbyl group. In other metal salt. Within the methods to prepare the C-diimine embodiments, R“ represents a cyclic organyl group, a cyclic metal complexes, additional compounds including organyl group consisting of inert functional groups, or cyclic C-acylimine compounds and O-acylimine metal complexes hydrocarbyl group. Regardless of the structure of the orga can be intermediates and/or starting materials in the synthe 65 nyl group, organyl group consisting of inert functional sis of the C-diimine metal complexes. The C-diacyl com groups, or hydrocarbyl group, R“ can have any number of pounds, primary amines, C-acylimine compounds, carbon atoms as indicated herein. In some embodiments, the US 7,271,121 B2 7 8 C.-ketoaldehyde is a C to Co glyoxal; alternatively, a C to one, 1.2-cyclopentanedione, a Substituted 1.2-cyclopen Co glyoxal; or alternatively, a C to Ce glyoxal. In some tanedione, 1.2-cyclohexanedione, a Substituted 1.2-cyclo embodiments, the C-ketoaldehyde is phenylglyoxal or a hexanedione, 1.2-cycloheptanedione, and a Substituted 1.2- Substituted phenylglyoxal. In other embodiments, the O.-ke cycloheptanedione. In some Saturated cyclic C-dione toaldehyde is phenylglyoxal. Within substituted phenylgly- 5 embodiments, the C-dione can be 1.2-cyclopentanedione, a oxal, each Substituent can be a C to Cs organyl groups, a C Substituted 1.2-cyclopentanedione, 1.2-cyclohexanedione, to Cs organyl groups consisting of inert functional groups, or a substituted 1.2-cyclohexanedione. In some Saturated and/or a C to Cs hydrocarbyl groups. In other embodiments, cyclic C-dione embodiments, the C-dione can be 1.2-cyclo each phenyl substituents can be a C to Cs organyl groups pentanedione, or 1.2-cyclohexanedione. In yet other consisting of inert functional groups; or alternatively, a C to 10 embodiments, the C-dione can be 1.2-cyclopentanedione; or Cs hydrocarbyl groups. alternatively, 1.2-cyclohexanedione. A second class of C-diacyl compounds which can be used In Saturated ring system C-dione embodiments, the C-di in preparing C-diimine metal complexes is an O-dione (a one can be bicyclo2.2.1]hepta-1,2-dione, a Substituted bicy compound wherein two ketone oxygen atoms are bonded to clo2.2.1]hepta-1,2-dione, bicyclo[2.2.2]octa-1,2-dione, a adjacent carbon atoms). The C-diones utilized in the pro- 15 substituted bicyclo[2.2.2]octa-1,2-dione, O Call duction of the C-diimine metal complexes can be any phorquinone. In some saturated ring system embodiments, C-dione compound capable of reacting with two primary the C-dione can be bicyclo[2.2.1]hepta-1,2-dione, bicyclo amines to forman C-diimine compound. The C-dione can be 2.2.2]octa-1,2-dione, or camphorquinone. In yet other satu saturated, unsaturated, acyclic, cyclic, linear, branched, aro rated ring system C-dione embodiments, the C-dione can be matic, and/or heteroaromatic. k 2O camphorquinone. Generally, the O.-dione will have the structure R—C In unsaturated cyclic C-dione embodiments, the C-dione (=O)—C(=O) R' wherein the structures of R'' and R' can be 1,2-benzoquinone, a Substituted 1,2-benzoquinone, are independent of each other and can be an organyl group, cyclohex-3-ene-1,2-dione, a Substituted cyclohex-3-ene-1, an organyl group consisting of inert functional groups, or a 2-dione, cyclopent-3-ene-1,2-dione, a Substituted cyclopent hydrocarbyl group. In embodiments, R'' and/or R' can be 25 3-ene-1,2-dione, a cyclohex-4-ene-1,2-dione, a Substituted a C to Cao organyl group; alternatively, a C to Cao organyl cyclohex-4-ene-1,2-dione, 3,4-dihydro-1,2-naphtho group consisting of inert functional groups; alternatively, a quinone, a Substituted 3,4-dihydro-1,2-naphthaquinone, 1,4- C to Co. hydrocarbyl group; alternatively, a C to Co dihydronaphthoduinone, or a substituted 1,4-dihydronaph organyl group; alternatively, a C to Cao organyl group thoduinone. In some unsaturated cyclic C-dione consisting of inert functional groups; alternatively, a C to 30 embodiments, the C-dione can be 1,2-benzoquinone, cyclo C., hydrocarbyl group; alternatively, a C, to Co organyl hex-3-ene-1,2-dione, cyclopent-3-ene-1,2-dione, cyclohex group; alternatively, C to Co organyl group consisting of 4-ene-1,2-dione, 3,4-dihydronaphthoguinone, or 1,4-dihy inert functional groups; alternatively, a C to Co. hydrocar dronaphthoduinone. In other unsaturated ring C-dione byl group; alternatively, a C to Cs organyl group; alterna embodiments, the C-dione can be 1,2-benzoquinone; alter tively, a C to Cs organyl group consisting of inert functional 35 natively, 3,4-dibydronaphthoduinone; or alternatively, 1,4- groups; or alternatively, a C to Cs hydrocarbyl group. dihydronaphthano-quinone. In some embodiments, the C-dione is an acyclic C-dione; In aromatic ring system C-dione embodiments, the C-di both R'' and R'' are acyclic. In other embodiments, C-dione one can be a 1.2-naphthoduinone, a substituted 1.2-naph can be a semi-cyclic C-dione; R'' and/or R' are, or com thoduinone, 2.3-naphthoduinone, a Substituted 2.3-naphtho prise, a cyclic structure but are not connected through a ring 40 quinone, acenaphthenequinone, a Substituted or ring system. In yet other embodiments, the C-dione is a acenaphthenequinone, phenanthrenequinone, a Substituted cyclic C-dione; R'' and R'' are connected to form a ring or phenanthrenequinone, pyrenequinone, or a Substituted ring system containing both carbon atoms of the C-dione pyrenequinone. In some aromatic ring system C-dione group. In some semi-cyclic and/or cyclic C-dione embodi embodiments, the C-dione can be 1.2-naphthoduinone, 2.3- ments, the ring or ring system can be saturated. In other 45 naphthoduinone, acenaphthenequinone, phenanthrene semi-cyclic and/or cyclic C-dione embodiments, the ring or quinone, or pyrenequinone. In other aromatic ring system ring system can contain carbon-carbon double bonds. In C-dione embodiments, the C-dione can be acenaphthene further semi-cyclic and/or cyclic C-dione embodiments, the quinone, phenanthrenequinone, or pyrenequinone. In yet ring system can be a bicyclic ring system. In yet other other aromatic ring system C-dione embodiments, the C-di semi-cyclic and/or cyclic C-dione embodiments, the ring or 50 one can be 1.2-naphthoguinone; alternatively, 2.3-naphtho ring system can comprise an aromatic ring or an aromatic quinone; alternatively, acenaphthenequinone; alternatively, ring structure. phenanthrenequinone; or alternatively, pyrenequinone. In acyclic C-dione embodiments, the C-dione can be Within the substituted C-dione embodiments, each sub 2,3-butanedione, a substituted 2,3-butanedione, 2,3-pen stituent can independently be an organyl group, an organyl tanedione, a Substituted 2,3-pentanedione, 2.3-hexanedione, 55 group consisting of inert functional groups, a hydrocarbyl a Substituted 2.3-hexanedione, 3,4-hexanedione, or a Sub group, or an inert functional group. In some embodiments, stituted 3,4-hexanedione. In some embodiments, the C-di the organyl Substituent(s) can be a C to Co organyl group, one can be 2,3-butanedione, 2,3-pentanedione, 2.3-hex a C to Co organyl group consisting of inert functional anedione, or 3,4-hexanedione. In further embodiments, the groups, or a C to Co. hydrocarbyl group. In some Substi C-dione can be 2,3-butanedione; alternatively, 2,3-pen- 60 tuted C-dione embodiments, the Substituents can be a C to tanedione; alternatively, 2.3-hexanedione; or alternatively, Co organyl group, a C to Co organyl group consisting of 3,4-hexanedione. inert functional groups, or a C to Cohydrocarbyl group. In In aromatic semi-cyclic C-dione embodiments, the C-di other substituted C-dione embodiments, the substituent(s) one can be benzil or a substituted benzil. In other embodi can be a C to Cs organyl group, a C to Cs organyl group ments, the C-dione can be benzil. 65 consisting of inert functional groups, or a C to Cs hydro In Saturated cyclic C-dione embodiments, the C-dione can carbyl group. In further substituted C-dione embodiments, be 1.2-cyclobutanedione, a substituted 1.2-cyclobutanedi the Substituent(s) can be a C to Co organyl group; alter US 7,271,121 B2 9 10 natively, a C to Co organyl group; alternatively, a C to Cs organyl group; alternatively, a C to Cao organyl group TABLE 1-continued consisting of inert functional groups; alternatively, a C to C, organyl group consisting of inert functional groups: Example C-Diacyl Compounds alternatively, a C to Cs organyl group consisting of inert 5 O O functional groups; alternatively, a C to Cao hydrocarbyl ( 13 group; alternatively, a C to Co. hydrocarbyl group; alter R R natively, a C to Cs hydrocarbyl group; or alternatively, an inert functional group. Independent of the carbon number of 10 R 2 R 14 the organyl group, organyl group consisting of inert func Structure 3 tional groups, and hydrocarbyl group, each organyl group, O O organyl group consisting of inert functional groups, and hydrocarbyl group Substituent can be a primary, secondary, R R13 tertiary, or quaternary hydrocarbyl group. In some embodi- R12 R 14 ments, each organyl group, organyl group consisting of inert functional groups, and hydrocarbyl group can be a primary sia. group; alternatively, a secondary group; alternatively, a tertiary group; or alternatively, a quaternary group. Indepen- O O dent of the carbon number of the organyl group consisting of inert functional groups, the organyl group consisting of R R13 inert functional groups can comprise a halides, ether groups, R12 R 14 or Sulfide groups. In some embodiments, the organyl group R15 R17 consisting of inert functional groups can be a trifluoromethyl 25 R16 R18 group; or alternatively, a trichloromethyl group. Indepen- Structure 5 dent of the carbon number of the hydrocarbyl group, each R9 R20 hydrocarbyl group Substituent can independently be a methyl, ethyl, n-propyl (1-propyl), isopropyl (2-propyl), 30 O R R17 n-butyl (1-butyl), sec-butyl (2-butyl), isobutyl (2-methyl-1- R18 propyl), tert-butyl (2-methyl-2-propyl), n-pentyl (1-pentyl), s 5 2-pentyl, 3-pentyl, 2-methyl-1-butyl, tert-pentyl (2-methyl- R 2-butyl), 3-methyl - 1-butyl, 3-methyl-2-butyl-neo-pentyl O R R16 (2,3-dimethyl-1-propyl), or n-hexyl (1-hexyl) group. In is Structure 6 embodiments, inert functional group can be a halogen atom O O or an alkoxy group; alternatively, a halogen atom; or alter natively, an alkoxy group. In some embodiments, the halo gen atom may be fluorine, chlorine, bromine or iodine; R31 R32 alternatively, chlorine; or alternatively, fluorine. In some 40 embodiments, the alkoxy group can be a methoxy group; R33 R34 alternatively, an ethoxy group; alternatively, an isopropoxy Structure 7 group; or alternatively, a tert-butoxy group. In embodiments, the C-diacyl compounds can have any Structure as indicated in Table 1. In other embodiments, the 45 O O diacyl compound can have Structure 2, 3, 4, or 5; alterna tively, Structure 6; alternatively, Structure 7, 8, or 9; alter- 31 32 natively, structure 10, 11, or 12; or alternatively, Structure R R 10. 50 R35 R36 TABLE 1.

Example C-Diacyl Compounds R 37 R38 Structure 8 O O 55

R1 R2 O O Structure 1 R40

R R 14 R39 R12 (CH2) R41 R43 Structure 2 65 Structure 9 US 7,271,121 B2 11 12 synthesis of an O-acylimine compound, O-acylimine metal TABLE 1-continued complex, C-diimine compound, and/or C-diimine metal complex as described herein. The O-acylimine compound, Example C-Diacyl Compounds C-acylimine metal complex, C-diimine compound, and/or O O C-diimine metal complexes can be produced using any method described herein. Minimally, the primary amine comprises an —NH R R52 group. In a further embodiment, the primary amine com prises an —NH group and an organyl group; alternatively, 10 comprises an —NH group and a metal salt complexing group; alternatively, comprises an —NH2 group, a metal salt R53 R54 complexing group and a linking group linking the metal salt R55 R56 complexing group to the —NH group; alternatively, com Structure 10 prises an —NH group and an organyl group consisting of 15 inert functional groups; or alternatively, comprises an NH, O O group and a hydrocarbyl group. In yet other embodiments, R51 R52 the primary amine consists of an —NH group and an organyl group; alternatively, consists of an —NH group, a metal salt complexing group and a linking group linking the metal salt complexing group to the —NH group; alterna tively, consists of an —NH group and an organyl group R55 R57 R58 R56 consisting of inert functional groups; or alternatively, con Structure 11 sists of an —NH group and a hydrocarbyl group. The

primary amines can be saturated, unsaturated, linear, 25 branched, acyclic, cyclic, aromatic, and/or heteroaromatic. In an aspect, the primary amine can comprise an —NH group and organyl group; or alternatively, the primary amine can consist of an —NH group and an organyl group. In the embodiments wherein the primary amine can comprise or 30 consist of an —NH group and organyl group, the organyl group can be a C to Co organyl group; alternatively, a C to Cao organyl group; alternatively, a C to Co organyl R60 group; or alternatively, a C to Cs organyl group. The Structure 12 organyl group can be saturated, unsaturated, linear, 35 branched, acyclic, cyclic, aromatic, and/or heteroaromatic. Within the Structures of Table 1, R', R. R'' to/through In some embodiments, the primary amine comprising or R, R to/through R', and R to/through R' can each consisting of an —NH group and organyl groups can have independently be hydrogen, an organyl group, an organyl Structure 1a indicated below: group consisting of inert functional groups, or a hydrocarbyl RNH, Structure 1a group. The organyl group, organyl group consisting of inert 40 functional groups, and hydrocarbyl group are generally wherein R' represents the organyl group. In embodiments, described within the description of the C-diacyl compounds that utilize a second primary amine comprising or consisting and can have any embodiment as described therein. In of an —NH group and organyl groups, the second primary Structure 2, “p' can be a whole integer ranging from 1 to 10; amine comprising or consisting of an —NH group and alternatively, a whole integer ranging from 1 to 3; alterna 45 organyl groups can be designated as having Structure 2a tively, 1 ; alternatively, 2; or alternatively, 3. In some indicated below: embodiments, R. R. R'' to/through R', R' to/through R, and R to/through R' can be hydrogen. In some RNH, Structure 2a embodiments, the C-diacyl compound may have Structure 1 where R' is an organyl group, an organyl group consisting 50 wherein R' represents the organyl group. of inert functional groups, or a hydrocarbyl group, and R is In an aspect, the primary amine can comprise an —NH hydrogen. group and an organyl group consisting of inert functional groups; or alternatively, the primary amine can consist of an Primary Amines —NH group and an organyl group consisting of inert The primary amine(s) that can be utilized in the synthesis 55 functional groups. In the embodiments wherein the primary of the C-diimine metal complexes (and/or the intermediate amine can comprise or consist of an —NH group and an C-acylimine compounds, C-acylimine metal complexes) can organyl group consisting of inert functional groups, the be any primary amine capable of forming an imine group organyl group consisting of inert functional groups can be a when contacted with an acyl group. It should be noted that C to Co organyl group consisting of inert functional while the applicable primary amines are described in terms 60 groups; alternatively, a C to Cao organyl group consisting of of the ability to form an imine group when contacted with an inert functional groups; alternatively, a C to Co organyl acyl group, Such description is not intended to imply a group consisting of inert functional groups; or alternatively, method by which an imine group of an O-acylimine com a C to Cs organyl group consisting of inert functional pound, O-acylimine metal complex, C.-diimine compound, groups. The organyl group consisting of inert functional and/or C-diimine metal complex described herein are made. 65 groups can be Saturated, unsaturated, linear, branched, acy The language is intended to describe, to one skilled in the clic, cyclic, aromatic, and/or heteroaromatic. In some art, the particular primary amine(s) that can be utilized in the embodiments, the inert functional groups can be ether US 7,271,121 B2 13 14 groups; alternatively, sulfide groups; alternatively, halide atoms; or alternatively, hydrocarbyl groups. In some embodiments, the primary amine comprising or consisting Structure 4a of an -NH group and an organyl group consisting of inert Ra12' Rall' functional groups can have Structure 1a wherein R' repre sents the organyl group consisting of inert functional groups. In embodiments that utilize a second primary amine com prising or consisting of an —NH group and an organyl group consisting of inert functional groups, the second Ral4 Rals' primary amine comprising or consisting of an -NH group 10 and an organyl group consisting of inert functional groups can be designated as having Structure 2a wherein R' wherein R'' to/through R' represent the substituents of represents the organyl group consisting of inert functional the aromatic ring. groups. In an aspect, the primary amine can comprise an -NH2 In some embodiments, the organyl group consisting of 15 group and hydrocarbyl group; or alternatively, the primary inert functional groups can be an aromatic ring or aromatic amine can consist of an —NH2 group and a hydrocarbyl ring system having one or more inert functional group group. In embodiments wherein the primary amine can substituent(s). In these embodiments, the aromatic ring or comprise or consist of an —NH2 group and hydrocarbyl aromatic ring system can be a substituted benzene ring (a group, the hydrocarbyl group can be a C to Cao hydrocarbyl substituted phenyl group); or alternatively, a substituted group; alternatively, a C to Co. hydrocarbyl group; alter naphthalene ring (a substituted naphthyl group). The aro natively, a C to Cohydrocarbyl group; or alternatively, a C matic ring or aromatic ring system inert functional group to C. hydrocarbyl group. Independently, the hydrocarbyl substituent(s) can be an organyl group having halogen group can be a saturated, unsaturated, acyclic, cyclic, linear, atoms, an ether group (alkoxy group or etheryl group), or a branched, and/or aromatic. In some embodiments, the pri sulfide group (sulfidyl group). In some embodiments, the 25 mary amine comprising or consisting of an -NH2 group aromatic ring inert functional group substituent(s) can be a and a hydrocarbyl group can have Structure 1a wherein R' trifluoromethyl group, a C to Cs ether group a C to Cs represents the hydrocarbyl group. In embodiments that sulfide group or a halogen atom. In some embodiments, the utilize a second primary amine comprising or consisting of halogen atom may be fluorine, chlorine, bromine or iodine; an -NH group and an hydrocarbyl group, the second alternatively, chlorine; or alternatively, fluorine. In some 30 primary amine comprising or consisting of an -NH2 group embodiments, the alkoxy group can be a methoxy group: and an hydrocarbyl group can be designated as having alternatively, an ethoxy group; alternatively, an isopropoxy Structure 2a wherein R' represents the hydrocarbyl group. group; or alternatively, a tert-butoxy group. Non-limiting Acyclic hydrocarbyl group embodiments can include C1 examples of a primary amine consisting of an aromatic ring to Co acyclic hydrocarbyl groups; alternatively, C to Co having one or more inert functional groups include substi 35 acyclic hydrocarbyl groups; alternatively, C to Co acyclic tuted anilines wherein the substituents can be the substitu hydrocarbyl groups; or alternatively, C to Cs acyclic hydro ents as described above. Non-limiting examples are primary carbyl groups. The acyclic hydrocarbyl groups can be linear; amines consisting of an aromatic ring or aromatic ring or alternatively, branched. Independent of the carbon num systems having one or more inert functional groups such as ber of the acyclic hydrocarbyl group, the acyclic hydrocar 40 byl group can be a primary, secondary, tertiary, or quaternary 2-methoxyaniline, 3-methoxyaniline, 4-methoxyanaline, hydrocarbyl group. In some embodiments, the acyclic 2-chloroaniline, 3-chloroaniline, 4-chloroanaline, 2-fluoroa hydrocarbyl group can be a primary hydrocarbyl group: niline, 3-fluoroaniline, 4-fluoroanaline, 2,6-trifluoromethy alternatively, a secondary hydrocarbyl group; alternatively, a laniline, or dimethyl-4-methoxyaniline. tertiary hydrocarbyl group; or alternatively, a quaternary In some embodiments, a primary amine comprising or 45 hydrocarbyl group. In an aspect, the acyclic hydrocarbyl consisting of an -NH group and an organyl group con groups can be a methyl, ethyl. n-propyl (1-propyl), isopropyl sisting of inert functional groups can have Structure 3a as (2-propyl), n-butyl (1-butyl), sec-butyl (2-butyl), isobutyl indicated below: (2-methyl-1-propyl), tert-butyl (2-methyl-2-propyl), n-pen tyl (1-pentyl), 2-pentyl, 3-pentyl, 2-methyl-1-butyl, tert 50 pentyl (2-methyl-2-butyl), 3-methyl-1-butyl, 3-methyl-2- Structure 3a butyl, neo-pentyl (2,3-dimethyl-1-propyl), or n-hexyl (1-hexyl) group. Specific, non-limiting, examples of primary amines consisting of an —NH group and an acyclic hydro Ral 3 NH carbyl groups include methyl amine, ethyl amine, n-propy 55 lamine, isopropyl amine, n-butyl amine, sec-butylamine (2-butylamine), isobutylamine (2-methyl-1-propylamine). Ral4 Ra15 tert-butylamine (2-methyl-2-propylamine), n-pentylamine. neopentylamine, and n-hexylamine. One skilled in the art will readily recognize which hydrocarbyl groups belong wherein R' to/through R' represent the substituents of 60 (and which amines have a hydrocarbyl group that belongs) the aromatic ring. In embodiments, that utilize a second to the primary, secondary, tertiary, or quaternary hydrocarbyl primary amine comprising or consisting of an -NH group group classes. and an organyl group consisting of inert functional groups, Cyclic hydrocarbyl group embodiments can include the second primary amine comprising or consisting of an embodiments wherein the hydrocarbyl group is cyclic (the NH, group and an organyl group consisting of inert func 65 NH, group is attached to a carbon that is a member of a tional groups can be designated as having Structure 4a ring or ring system) or embodiments wherein the hydrocar indicated below: byl group comprises a cyclic group (the -NH group is US 7,271,121 B2 15 16 attached to a carbon atom that is not a member of a ring or alternatively, a Substituted 2-maphthylamine; or alterna ring system). Regardless of whether the cyclic hydrocarbyl tively, a substituted benzyl amine. In other embodiments, the group is cyclic or comprises a cyclic group, the cyclic primary amine consisting of an —NH2 group and an aro hydrocarbyl group can be C to Co cyclic hydrocarbyl matic hydrocarbyl group can be aniline, 1-naphthylamine, group; alternatively, a C to Co cyclic hydrocarbyl group; or 2-naphthylamine, or benzyl amine. In yet other embodi alternatively, a C to Co cyclic hydrocarbyl group. In ments, the primary amine can be aniline; 1-naphthylamime; embodiments, the cyclic hydrocarbyl group can comprise a alternatively, 2-napthylamine; or alternatively, benzyl cyclobutyl group, a Substituted cyclobutyl group, a cyclo amine. In further embodiments, the primary amine can be pentyl group, a Substituted cyclopentyl group, a cyclohexyl aniline, or a Substituted aniline. In embodiments, the Sub group, a Substituted cyclohexyl group, a cycloheptyl group, 10 a Substituted cycloheptyl group, an adamantyl group, or a stituted aniline can be substituted at the 2-position. In some Substituted adamantyl group. In some embodiments, the embodiments, the substituted aniline is substituted at the 2 cyclic hydrocarbyl group can be a cyclobutyl group; alter and 6- position; alternatively, at the 2- and 5- position; or natively, a cyclopentyl group; alternatively, a cyclohexyl alternatively, at the 2-, 4-, and 6-positions. In other embodi group; alternatively, a cycloheptyl, or alternatively, an ada 15 ments, the Substituents at the 2- position, at the 2- and 6 mantyl group. In some embodiments, the primary amine position, at the 2- and 5- positions, or at the 2-, 4-, and 6 comprising an —NH2 group and cyclic hydrocarbyl group positions can independently be a primary Substituent; alter can be a Substituted cyclopentylamine, a Substituted cyclo natively; a secondary Substituent; alternatively, a tertiary hexylamine, a Substituted cyclohexylamine, or a substituted Substituent; or alternatively, a quaternary Substituent. In adamantylamine. In other embodiments, the primary amine Some embodiments, the primary amine consisting of an comprising or consisting of an —NH group and cyclic -NH group and an aromatic hydrocarbyl group can be hydrocarbyl group can be a substituted cyclopentylamine; 2,6-dimethylanaline, 2,6-diethylaniline, 2,6-diisopropyla alternatively, a Substituted cyclohexylamine; or alterna niline, or 2,6-di-tert-butylaniline. In other embodiments, the tively, a Substituted adamantylamine. In yet other embodi primary amine consisting of an —NH group and an aro ments, the primary amine comprising or consisting of an 25 matic hydrocarbyl group can be 2,6-dimethylanaline, 2.6- -NH group and cyclic hydrocarbyl group can be cyclo diethylaniline, or 2,6-dilsopropylaniline. In yet other pentylamine, cyclohexylamine, cycloheptylamine, or ada embodiments, the primary amine consisting of an —NH mantylamine. In yet other embodiments, the primary amine group and an aromatic hydrocarbyl group can be 2,6- consisting of a cyclic hydrocarbyl group can be cyclopen dimethylanaline; alternatively, 2,6-diethylaniline; alterna tylamine; alternatively, cyclohexylamine; or alternatively, 30 tively, 2,6-diisopropylaniline; alternatively, 2,6-di-tert-buty adamantylamine. lanaline; alternatively, 2,5-di-tert-butylanaline; alternatively, Aromatic hydrocarbyl group embodiments can include 2-isopropyl-6-methylanaline; or alternatively, 2,4,6-trim embodiments wherein the hydrocarbyl group is aromatic ethylanaline. (the —NH group is attached to a carbon that is a member of an aromatic ring or ring system) or embodiments wherein 35 In some embodiments, the primary amine comprising or the hydrocarbyl group comprises an aromatic group (the consisting of an —NH group and an aromatic hydrocarbyl —NH, group is attached to a carbon atom that is not a group can have Structure 3a wherein R' to/through R' member of a aromatic ring or aromatic ring system). Regard represent the Substituents of the aromatic hydrocarbyl group. less of whether the aromatic hydrocarbyl group of the In embodiments that utilize a second primary amine com primary amine is aromatic or comprises an aromatic group, 40 prising or consisting of an —NH group and an aromatic the aromatic hydrocarbyl group can be a C to Co aromatic hydrocarbyl group, the second primary amine comprising or hydrocarbyl group; alternatively, a C to Cao aromatic consisting of an —NH group and an aromatic hydrocarbyl hydrocarbyl group; or alternatively, a C to Co aromatic group can be designated as having Structure 4a wherein hydrocarbyl group. In some embodiments, the aromatic R'' to/through R' represent the substituents of the aro hydrocarbyl group can be a phenyl group, Substituted phenyl 45 matic hydrocarbyl group. group, a naphthyl group, a substituted naphthyl group, a In embodiments, each substituent of the cyclic hydrocar benzyl group, or a Substituted benzyl group. In other byl group or the aromatic hydrocarbyl group can indepen embodiments, the aromatic hydrocarbyl group can be a dently be a C to Co. hydrocarbyl group; alternatively, a C phenyl group, a naphthyl group, or a benzyl group. In yet to Co. hydrocarbyl group; or alternatively, a C to Cs other embodiments, the aromatic hydrocarbyl group is a 50 hydrocarbyl group. Independent of the carbon number of the phenyl group; alternatively, a naphthyl group; or alterna cyclic hydrocarbyl substituent, the substituents of the cyclic tively, a benzyl group. In further embodiments, the aromatic hydrocarbyl group or the aromatic hydrocarbyl group can be hydrocarbyl group can be a substituted phenyl group; alter primary, secondary, tertiary, or quaternary hydrocarbyl natively, a Substituted naphthyl group; or alternatively, a groups. In some embodiments, a cyclic hydrocarbyl Sub Substituted benzyl group. 55 stituent or an aromatic hydrocarbyl Substituent can be a In embodiments, the primary amine comprising an —NH primary hydrocarbyl group; alternatively, a secondary group and an aromatic hydrocarbyl group can be aniline, a hydrocarbyl group; alternatively, a tertiary hydrocarbyl Substituted aniline, 1-naphthylamine, a Substituted 1-naph group; or alternatively, a quaternary hydrocarbyl group. In thylamine, 2-naphthylamine, a Substituted 2-maphthylamine, Some embodiments, the cyclic hydrocarbyl group Substitu benzyl amine, or a Substituted benzyl amine. In some 60 ent or an aromatic hydrocarbyl Substituent can be a methyl, embodiments, the primary amine comprising an —NH ethyl, n-propyl (1-propyl), isopropyl (2-propyl), n-butyl group and an aromatic hydrocarbyl group can be a Substi (1-butyl), sec-butyl (2-butyl), isobutyl (2-methyl-1-propyl), tuted aniline, a Substituted 1-naphthylamine, a Substituted tert-butyl (2-methyl-2-propyl), n-pentyl (1-pentyl), 2-pentyl, 2-naphthylamine, or a Substituted benzyl amine. In other 3-pentyl, 2-methyl-1-butyl, tert-pentyl (2-methyl-2-butyl), embodiments, the primary amine comprising an —NH 65 3-methyl-1-butyl, 3-methyl-2-butyl, neo-pentyl (2,3-dim group and an aromatic hydrocarbyl group can be a Substi ethyl-1-propyl), or n-hexyl (1-hexyl) group. One skilled in tuted aniline; alternatively; a Substituted 1-naphtylamine; the art will readily recognize which cyclic hydrocarbyl US 7,271,121 B2 17 18 group Substituents or aromatic hydrocarbyl Substituents ing heteroatom of the metal salt complexing group. For belong to the primary, secondary, tertiary, or quaternary example, in 2-(2-aminoethyl)pyridine the linking group is hydrocarbyl group classes. —CH2CH2— and the metal salt complexing group is the In substituted phenyl group embodiments, the substituted 2-pyridinyl group, in 1-(2-aminoethyl)piperidine the linking phenyl hydrocarbyl group can be a 2-substituted phenyl group is —CH2CH2— and the metal salt complexing group group; alternatively, a 2,6-disubstituted phenyl group; alter is the 1-piperidinyl group, and in 2-aminopyridine the link natively, a 2.5-disubstituted phenyl group; or alternatively, a ing group is a bond and the metal salt complexing group is 2,4,6-trisubstituted phenyl group. In some embodiments, the the 2-pyridinyl group. Substituted phenyl hydrocarbyl group can be a 2,6-dimethy The metal salt complexing group, Q, can be any group iphenyl group, a 2,6-diethylphenyl group, a 2,6-diisopropy 10 comprising a heteroatom capable of complexing with the lphenyl group, or a 2,6-di-tert-butylphenyl group. In yet metal salt. In embodiments, the metal salt complexing group other embodiments, the substituted phenyl hydrocarbyl can be a C to Co group comprising a heteroatom; alterna group can be a 2,6-dimethyiphenyl group, a 2,6-diethylphe tively, a C to Co group comprising a heteroatom; alterna nyl group, or a 2,6-diisopropylphenyl group. In further tively, a C to Co group comprising a heteroatom; or embodiments, the Substituted phenyl hydrocarbyl group can 15 alternatively, a C to C group comprising a heteroatom. In be a 2,6-dimethyiphenyl group; alternatively, a 2,6-diethy Some embodiments, the metal salt complexing heteroatom iphenyl group; alternatively, a 2,6-diisopropylphenyl group; of the metal salt complexing group can be oxygen, Sulfur, alternatively, a 2,6-di-tert-butyiphenyl group; alternatively, a nitrogen, or phosphorus. In other embodiments, the metal 2,5-di-tert-butylphenyl group; alternatively, a 2-isopropyl salt complexing heteroatom of the metal salt complexing 6-methyl group; or alternatively, a 2.4.6-trimethylphenyl group can be oxygen or Sulfur. In yet other embodiments, the group (mesityl group). metal salt complexing heteroatom of the metal salt com In an embodiment, the primary amine can comprise an plexing group can be nitrogen, or phosphorus. In further —NH, group and a metal salt complexing group. In another embodiments, the metal salt complexing heteroatom of the embodiment, the primary amine can comprise an —NH metal salt complexing group can be oxygen; alternatively, group, a metal salt complexing group, and a linking group 25 Sulfur, alternatively, nitrogen; or alternatively, phosphorus. linking the metal salt complexing group to the —NH2 group. Optionally, the metal salt complexing group can contain In yet another aspect the primary amine can consist of a additional heteroatom which do not complex the metal salt metal salt complexing group, and a linking group linking the in C-diimine metal complex Such as inert heteroatoms (e.g. metal salt complexing group to the —NH group. Generally, halides, and silicon) and/or additional metal salt complexing the metal salt complexing group and the linking group are 30 heteroatom(s) which do not complex with the metal salt. independent elements. Thus, the primary amine comprising In particular embodiments, the metal salt complexing or consisting of an —NH group, a metal salt complexing group can be a dialkyl aminyl group, a diphenyl aminyl group, and a linking group linking the metal salt complexing group, a Substituted diphenyl aminyl group, an alkyl phenyl group to the -NH group can be described using any aminyl group, an alkyl Substituted phenyl aminyl group, a combination of the metal salt complexing group described 35 dialkyl phosphinyl group, a diphenyl phosphinyl group, a herein and the linking group linking the metal salt complex Substituted diphenyl phosphinyl group, an alkyl phenyl ing group to the —NH group described herein. phosphinyl group, an alkyl Substituted phenyl phosphinyl In embodiments, the primary amine comprising or con group, an alkyl etheryl group, a phenyl etheryl group, a sisting of an —NH group, a metal salt complexing group, Substituted phenyl etheryl group, an alkyl sulfidyl group, a 40 phenyl Sulfidyl group, a Substituted phenyl sulfidyl group, a and a linking group linking the metal salt complexing group furanyl group, a Substituted furanyl group, a thiophenyl to the NH group can have Structure 5a: group, a Substituted thiophenyl group, a tetrahydrofuranyl Q—L-NH2 Structure 5a group, a Substituted tetrahydrofuranyl group, a thiophanyl group, a Substituted thiophanyl group, a pyridinyl group, a where Q represents the metal salt complexing group and L 45 Substituted pyridinyl group, a morphilinyl group, a Substi represents the linking group. In some embodiments, the tuted morphilinyl group, a pyranyl group, a Substituted metal salt complexing group and the linking group can have pyranyl group, a tetrahydropyranyl group, a Substituted structures indicated in Table 2 and Table 3, respectively. tetrahydropyranyl group, a quinolinyl group, a Substituted The metal salt complexing group, Q, can be any group quinolinyl group, a pyrrolyl group, a Substituted pyrrolyl comprising a heteroatom capable of complexing with the 50 group, a pyrrolidinyl group, a Substituted pyrrolidinyl group, metal salt. The linking group, L, can be any group capable a piperidinyl group, or a Substituted piperidinyl group. In of linking the metal salt complexing group to the —NH embodiments, the metal salt complexing group can be a group. The linking group includes all atoms between the dialkyl aminyl group, a diphenyl aminyl group, a dialkyl primary amine nitrogen atom, the -NH2, and the metal salt phosphinyl group, a diphenyl phosphinyl group, an alkyl complexing group. If the metal salt complexing group is 55 etheryl group, a phenyl etheryl group, an alkyl Sulfidyl acyclic, the linking group includes all atoms between the group, a phenyl sulfidyl group, a furanyl group, a thiophenyl primary amine nitrogen atom and the heteroatom of the group, a tetrahydrofuranyl group, a thiophanyl group, a metal salt complexing functional group. For example, in pyridinyl group, a morphilinyl group, a pyranyl group, a N,N-dimethylethylenediamine the linking group is tetrahydropyranyl group, a quinolinyl group, a pyrrolyl —CH2CH2— and the metal salt complexing group is the 60 group, a pyrrolidinyl group, or a piperidinyl group. In some N,N-dimethylaminyl group, and in 2-phenoxyethylamine embodiments, the metal salt complexing group can be a the linking group is —CH2CH2— and the metal salt com dialkyl aminyl group, a diphenyl aminyl group, a Substituted plexing group is the phenoxy group. However, if the het diphenyl aminyl group, a dialkyl phosphinyl group, a diphe eroatom of the metal salt complexing group is contained nyl phosphinyl group, a Substituted diphenyl phosphinyl within a ring, the linking group includes all the atoms 65 group, an alkyl etheryl group, a phenyl etheryl group, a between the primary amine nitrogen atom and the first atom Substituted phenyl etheryl group, an alkyl sulfidyl group, a contained within the ring containing the metal salt complex phenyl Sulfidyl group, a Substituted phenyl sulfidyl group, a US 7,271,121 B2 19 20 pyridinyl group, a Substituted pyridinyl group, a morphilinyl Co hydrocarbyl group; or alternatively, a C to Cs hydro group, or a substituted morphilinyl group; alternatively, a carbyl group. The Substituted phenyl groups of the aminyl, dialkyl aminyl group, a diphenyl aminyl group, a dialkyl phosphinyl, ethyl, or sulfidyl metal salt complexing group phosphinyl group, a diphenyl phosphinyl group, an alkyl embodiments can independently be a C to Co. phenyl etheryl group, a phenyl etheryl group, an alkyl Sulfidyl group; or alternatively, a C to Cs phenyl group. Indepen group, a phenyl Sulfidyl group, a pyridinyl group, or a dently, the alkyl groups of the aminyl, phosphinyl, ethyl, or morphilinyl group; alternatively, a dialkyl aminyl group, a Sulfidyl metal salt complexing groups can be primary, sec diphenyl aminyl group, a Substituted diphenyl aminyl group, ondary, tertiary, or quaternary hydrocarbyl groups. In some a dialkyl phosphinyl group, a diphenyl phosphinyl group, or embodiments, the alkyl group of the aminyl, phosphinyl, a Substituted diphenyl phosphinyl group; alternatively, a 10 ethyl, or Sulfidyl metal salt complexing group can be a dialkyl aminyl group, a diphenyl aminyl group, a dialkyl primary hydrocarbyl group; alternatively, a secondary phosphinyl group, a diphenyl phosphinyl group; or alterna hydrocarbyl group; alternatively, a tertiary hydrocarbyl tively, a diphenyl aminyl group, a Substituted diphenyl group; or alternatively, a quaternary hydrocarbyl group. aminyl group, a diphenyl phosphinyl group, a Substituted Each substituent of the substituted metal salt complexing diphenyl phosphinyl group; alternatively, a diphenyl aminyl 15 group embodiments can independently be a C to Co group, a Substituted diphenyl aminyl group, a diphenyl organyl group, a C to Co organyl group consisting of inert phosphinyl group, a Substituted diphenyl phosphinyl group, functional groups, a C to Cohydrocarbyl group, or an inert a phenyl Sulfidyl group, a Substituted phenyl sulfidyl group, functional group. In some embodiments, the Substituents of a pyridinyl group, or a Substituted pyridinyl group; or the Substituted metal salt complexing group can be C to Cs alternatively, a diphenyl aminyl group, a diphenyl phosphi organyl groups, a C to Cs organyl groups consisting of inert nyl group, a phenyl sulfidyl group, or a pyridinyl group. In functional groups, C to Cs hydrocarbyl groups, or an inert other embodiments, the metal salt complexing group can be functional group. In other embodiments, the Substituents of a dialkyl aminyl group or a dialkyl phosphinyl group; the Substituted metal salt complexing group can be C to Co alternatively, a diphenyl aminyl group or a diphenyl phos organyl groups; alternatively, a C to Co organyl groups phinyl group; alternatively, a Substituted diphenyl aminyl 25 consisting of inert functional groups; alternatively, a C to group or a substituted diphenyl phosphinyl group; alterna C. hydrocarbyl groups; alternatively, a C, to Cs organyl tively, a 2-pyridinyl group or a Substituted 2-pyridinyl groups; alternatively, a C to Cs hydrocarbyl groups; or group; alternatively, an alkyl etheryl group, a phenyl etheryl alternatively, inert functional groups. Independent of the group, a Substituted phenyl etheryl group, a alkyl Sulfidyl carbon number of the organyl group, and the organyl group group, a phenyl sulfidyl group, or a Substituted Sulfidyl 30 consisting of inert functional groups each organyl group and group; alternatively, an alkyl etheryl group or an alkyl organyl group consisting of inert functional groups can be a sulfidyl group; alternatively, a phenyl etheryl group, a sub primary, secondary, tertiary, or quaternary hydrocarbyl stituted phenyl etheryl group, a phenyl Sulfidyl group, or a group. In some embodiments, each organyl group and orga substituted sulfidyl group; alternatively, a phenyl etheryl nyl group consisting of inert functional groups can be a group or a Substituted phenyl etheryl group; alternatively, a 35 primary group; alternatively, a secondary group; alterna phenyl Sulfidyl group, a Substituted phenyl sulfidyl group; tively, a tertiary group; or alternatively, a quaternary group. alternatively, a phenyl Sulfidyl group; alternatively, a Sub Independent of the carbon number of the organyl group stituted phenyl Sulfidyl group; alternatively, a furanyl group, consisting of inert functional groups, the organyl group a Substituted furanyl group, a thiophenyl group or a Substi consisting of inert functional groups can comprise a halide, tuted thiophenyl group; alternatively, a 1-morphilinyl group 40 an ether group (alkoxy group or etheryl group), or a sulfide or a Substituted 1-morphilinyl group; alternatively, a 2-mor group (sulfidyl group). In some embodiments, the organyl philinyl group or a substituted 2-morphilinyl group; alter group consisting of inert functional groups can be a trifluo natively, a 2-pyranyl group or a Substituted 2-pyranyl group; romethyl group; or alternatively, a trichloromethyl group. In alternatively, a 2-tetrahydropyranyl group, a Substituted embodiments, the inert functional group can be a halogen 2-tetrahydropyranyl group; alternatively, a 1-piperidinyl 45 atom or an alkoxy group; alternatively, a halogen atom; or group, or a Substituted 1-piperidinyl group; alternatively, a alternatively, an alkoxy group. In some embodiments, the 1-pyrrolidinyl group, a Substituted 1-pyrrolidinyl group; halogen atom may be fluorine, chlorine, bromine or iodine; alternatively, a 2-pyrrolidinyl group, a Substituted 2-pyrro alternatively, chlorine; or alternatively, fluorine. In some lidinyl group; alternatively, a 2-piperidinyl group, or a embodiments, the alkoxy group can be a methoxy group; Substituted 2-piperidinyl group; alternatively, a 2-quinolinyl 50 alternatively, an ethoxy group; alternatively, an isopropoxy group or a substituted 2-quiolinyl group; alternatively, a group; or alternatively, a tert-butoxy group. 1-pyrrolyl group or a Substituted 1-pyrrolyl group; alterna Independent of the carbon number of the hydrocarbyl tively, a 2-pyrrolyl group or a Substituted 2-pyrrolyl group; substituent, the alkyl group or the substituent(s) of the alternatively, a 2-tetrahydrofuranyl group or a Substituted Substituted metal salt complexing group can be a primary, 2-tetrahydrofuranyl group; or alternatively, a 2-thiophanyl 55 secondary, tertiary, or quaternary hydrocarbyl group. In group or a Substituted 2-thiophanyl group. In yet other Some embodiments, the alkyl group or the Substituent(s) of embodiments, the metal salt complexing group can be a the Substituted metal salt complexing group can be a primary diphenyl aminyl group; alternatively, a Substituted diphenyl hydrocarbyl group; alternatively, a secondary hydrocarbyl aminyl group; alternatively, a diphenyl phosphinyl group; or group; alternatively, a tertiary hydrocarbyl group; or alter alternatively, a Substituted diphenyl phosphinyl group. 60 natively, a quaternary hydrocarbyl group. In some embodi The alkyl group(s) of the aminyl, phosphinyl, ethyl, or ments, the alkyl group or the hydrocarbyl substituents of the Sulfidyl metal salt complexing group embodiments can Substituted metal salt complexing group can be a methyl, independently be a C to Co organyl group consisting of ethyl, n-propyl (1-propyl), isopropyl (2-propyl), n-butyl inert functional groups; alternatively, a C to Co organyl (1-butyl), sec-butyl (2-butyl), isobutyl (2-methyl-1-propyl), group consisting of inert functional groups; or alternatively, 65 tert-butyl (2-methyl-2-propyl), n-pentyl (1-pentyl), 2-pentyl, a C to Cs organyl group consisting of inert functional 3-pentyl, 2-methyl-1-butyl, tert-pentyl (2-methyl-2-butyl), groups; C to Co. hydrocarbyl group; alternatively, a C to 3-methyl-1-butyl, 3-methyl-2-butyl, neo-pentyl (2,3-dim US 7,271,121 B2 21 22 ethyl-1-propyl), or n-hexyl (1-hexyl) group. One skilled in amine comprising a metal salt complexing group can be the art will readily recognize which alkyl group or the N,N-dimethyl-ethylenediamine; alternatively, N,N-diethyl hydrocarbyl substituents of the substituted metal salt com ethylenediamine; alternatively, N,N-diphenylethylene-di plexing group belong to the primary, secondary, tertiary, or amine; alternatively, 2-(diphenylphosphino)ethylamine; quaternary hydrocarbyl group classes. alternatively, 3-(diphenylphosphino)-propylamine; alterna The linking group linking the metal salt complexing tively, 2-(aminomethyl)pyridine; alternatively, 2-(2-amino group to the -NH group can be a bond, an organyl group, ethyl)pyridine; or alternatively, 2-aminoethyl-(4-chlorophe and organyl group consisting of inert functional groups, or nyl)sulfide. a hydrocarbyl group. In other embodiments, the linking In some embodiments, the metal salt complexing group group can be a bond; alternatively, an organyl group; alter 10 can have any Structure indicated in Table 2. In some natively, an organyl group consisting of inert functional embodiments, the metal salt complexing group can have groups; or alternatively, a hydrocarbyl group. In some Structure 1c or Structure 2c. In other embodiments, the embodiments, the linking group can be a C to Co organyl metal salt complexing group can have Structure 3c or group; or alternatively, a C to Cs organyl group. In some Structure 4c: alternatively, Structure 5c or Structure 6c; embodiments, the linking group linking the metal salt com 15 alternatively, Structure 8c or Structure 9c; alternatively, plexing group to the -NH group can be a C to Co organyl group consisting of inert functional groups; or alternatively, TABLE 2 a C to Cs organyl group consisting of inert functional groups. In other embodiments, the linking group linking the Example Metal salt complexing Groups metal salt complexing group to the —NH group can be a C ORc to Co. hydrocarbyl group; or alternatively, a C to Cs Structure 1c hydrocarbyl group. SR Structure 2c In some embodiments, the hydrocarbyl linking group can NReRc8 be —(CRR), where R and R are independently Structure 3c hydrogen, methyl, ethyl, propyl, isopropyl, or butyl groups 25 PRc5Rc6 and m can be an integer from 1 to 5. In other embodiments, Structure 4c the linking group can be a methylene group (—CH2—), an ethylene group (-CHCH ), a propyl group Rc Rc13 (—CH2CH2CH2—), a -CH(CH)CH2— group, Rc15 —C(CH) group, or abutylene group (-CHCHCH 30 CH2—). In some non-limiting embodiments, the linking -N Rc17 Rc18 group can be a methylene group (-CH2—), an ethylene Rc12 Rc16 group (-CHCH ), or a propylene group RC 14 (—CH2CH2CH2—); or alternatively, an ethylene group Structure 5c (—CHCH ), or a propylene group (-CHCHCH ). 35 In yet other embodiments, the linking group can be a Rc3 Rc15 methylene group; alternatively, an ethylene group; or alter Rc11 Rc17 natively, a propylene group. Rc19 -N In embodiments, the primary amine comprising a metal c20 salt complexing group can be 1-(2-aminoethyl)pyrrolidine, 40 Rc12 R 2-(2-aminoethyl)piperdine, 2-(2-aminoethyl)pyrrolidine, Rc18 N,N-dimethyl-ethylenediamine, N,N-diethylethylenedi Rc14; Rc16: amine, N,N-diphenylethylenediamine, 2-(aminomethyl)-py Structure 6c ridine, 2-(2-aminoethyl)pyridine, 2-(diphenylphosphino) 3 Rc15 ethylamine, 3-(diphenylphosphino)-propylamine, 2-(2- 45 Rel Rc1 aminoethyl)furan, 2-(aminomethyl)furan, 2-(2-aminoethyl) -N Rc17 thiophene, 2-(aminomethyl)thiophene, 2-aminoethyl-(4- Rc12 O chlorophenyl)sulfide, 2-phenoxyethylamine, 2-methoxy Rc14SYS, Rc16 Rc18 ethylamine, 2-ethoxyethylamine, 2-isopropxyethylamine, Structure 7c and 1-(2-aminoethyl)piperidine. In some embodiments, the 50 primary amine comprising a metal salt complexing group Re Rc13 can be N,N-dimethylethylenediamine, N,N-diethylethylene diamine, N,N-diphenylethylenediamine, 2-(amino-methyl) pyridine, 2-(2-aminoethyl)pyridine, 2-(diphenylphosphino) ethylamine, 3-(diphenyl-phosphino)propylamine, 55 Rc18 2-aminoethyl-(4-chlorophenyl)sulfide, 2-phenoxyethy Rc16 lamine, 2-methoxy-ethylamine, 2-ethoxyethylamine, 2-and RC 14 isopropoxyethylamine. In yet other embodiments, the pri Structure 8c mary amine comprising a metal salt complexing group can Rc3 Rc15 be N,N-dimethylethylenediamine or N,N-diethylethylenedi 60 Roll Rc17 amine; alternatively, N,N-diphenylethylenediamine, Rc19 2-(diphenylphosphino)-ethylamine, 3-(diphenylphosphino) Rc21 -N propylamine; alternatively, 2-(aminomethyl)pyridine, 2-(2- Rc20 amino-ethyl)pyridine; alternatively, 2-aminoethyl-(4-chlo Rc18 rophenyl)sulfide; or alternatively, 2-phenoxy-ethylamine, 65 Rc14 Rc16 2-methoxyethylamine, 2-ethoxyethylamine, and 2-iso Structure 9c propxyethylamine. In further embodiments, the primary US 7,271,121 B2 23 24

TABLE 2-continued TABLE 2-continued Example Metal salt complexing Groups Example Metal salt complexing Groups

c5 R cll Rel 3 R

rty,O Rc14 Rc16 Rc18 10 Structure 10c Rc52 Rc54 Structure 18c.

15 Rc16 - C Rc62 Structure 19c.

Structure 12c 25 - C Rc63 Structure 20c Rel Rc13 Rc15

30

Rc14 Rc16 Rc18 Re79 Structure 13c N Rc80 35

Rc72 Rc78 -O Rc35

40 Rc74 Rc76 Structure 21c Rc32 Rc34 Structure 14c Rc3 Rc75 Rc3 Rc33 45 Rc71 Rc77 -S Rc35 Re79 P Rc80 Rc32 Rc34 Structure 15c 50 RC Rc72 Rc78

Rc74 Rc76 55 Structure 22c

Structure 11c or Structure 12c; alternatively, Structure 14c or Structure 15c., alternatively, Structure 19c or Structure 60 20c: or alternatively, Structure 21c or Structure 22c. In yet other embodiments, the metal salt complexing group can have Structure 3c; alternatively, Structure 4c: alternatively, Structure 7c: Structure 10c: alternatively, Structure 13c. 65 alternatively, Structure 16c; alternatively, Structure 17c: Structure 17c alternatively, Structure 18; alternatively, Structure 21c; or alternatively, Structure 22c. US 7,271,121 B2 25 26 Within the structures of Table 2, R', R. R. R.'' description, second description, etc., these labels do not to/through R', R to/through R, R-' to/through R', indicate a particular preference to the description of the R to/through R, R to/through R, R-7 to/through C-acylimine compounds. R" can each independently be hydrogen, an organyl group In a first description, the C-acylimine compound can be consisting of inert functional groups, a hydrocarbyl group, 5 minimally described as a compound comprising an or inert functional groups. In embodiments, R. R. R. C-acylimine group. In further embodiments, the R'' to/through R', R to/through R. R.' to/through C-acylimine compound can be described as a compound R, R to/through Re, R to/through R, R-71 comprising 1) an O-acylimine group and 2) an O-acylimine to/through R' of each Structure in Table 2 can indepen nitrogen group. In this first C-acylimine compound descrip 10 tion, the C-acylimine group can be further described as being dently be hydrogen, an organyl group consisting of inert derived from an O-diacyl compound. Thus, alternatively, the functional groups, a hydrocarbyl group, or an inert func C-acylimine compound can be described as compound com tional group and R' and Rican be a hydrocarbyl group. prising 1) an O-acylimine group derived from an O-diacyl In some embodiments, R. R. R. R.' to/through R', compound and 2) an O-acylimine nitrogen group; or alter R" to/through R, R-' to/through R, R to/through 15 natively, a compound consisting of 1) an O-acylimine group R, R to/through R, R-7 to/through R of each derived from an O-diacyl compound and 2) an O-acylimine Structure of Table 2 an independently be hydrogen, a C to nitrogen group. Co organyl group, a C to Co organyl group consisting of Within the C-acylimine compound, the O-acylimine inert functional groups, a C to Cohydrocarbyl group, a C group's nitrogen atom is derived from the primary amine's to Cs organyl group, a C to Cs organyl group consisting of —NH group and the C-acylimine compound's nitrogen inert functional groups, a C to Cs hydrocarbyl group or an group is derived from the remainder of the primary amine. inert functional group. The organyl groups, organyl groups Thus, the C-acylimine nitrogen group can have any of the consisting of inert functional groups, hydrocarbyl groups, embodiments as the primary amine (with the absence of the and inert functional groups are generally described within —NH group) as described herein. Therefore, the organyl the description of the metal complexing group descriptions 25 group, metal salt complexing group, linking group, organyl and can have any embodiment as described therein. group consisting of inert functional groups, and hydrocarbyl groups of the primary amine embodiments described herein In some embodiments, the linking group can have any are generally applicable to the description of the structure indicated in Table 3. Within the Structure of Table C-acylimine compound's nitrogen group with the proviso 3, the undesignated Valancies are the points of attachment 30 that the linking group links the metal salt complexing group for the -NH group and the metal salt complexing group: to the imine nitrogen atom of the C-acylimine group instead each R' can independently be hydrogen, a methyl group, or of the NH group of the primary amine. Thus, in embodi an ethyl group; and m can be an integer ranging from 1 to ments, the O-acylimine nitrogen group can comprise an 5. In further embodiments, m can be an integer ranging from organyl group; alternatively, comprise a metal salt complex 1 to 3; alternatively, m can be 2 or 3; alternatively, m can be 35 ing group; alternatively, comprise a metal salt complexing 1; alternatively, m can be 2: or alternatively, m can be 3. group and a linking group linking the metal salt complexing group to the C-acylimine nitrogen group nitrogen atom; TABLE 3 alternatively, comprise an organyl group consisting of inert Example Linking Groups functional groups; alternatively, comprise a hydrocarbyl 40 group; alternatively, consist of an organyl group; alterna —(CRR)- tively, consist of a metal salt complexing group and a linking Structure 1L group linking the metal salt complexing group to the -(CH2)- Structure 2L C-acylimine nitrogen group nitrogen atom; alternatively, —(CH2)— consist of an organyl group consisting of inert functional Structure 3L 45 groups; or alternatively, consist of a hydrocarbyl group. -(CH2CH2)— Additionally, as the C-acylimine group and the C-acylimine Structure 4L nitrogen group are derived from separate and independent elements, the C-diacyl compound and the primary amine, respectively, the O-acylimine compound can be further 50 described using any combination of the C-diacyl compound element described herein and the elements of the primary amine as described herein. In a second description, the O-acylimine compound can RL3 RL2 Structure SL be described as an O-acylimine compound product of con 55 tacting an O-diacyl compound with a primary amine. Within this second O-acylimine compound description, as in the In embodiments, the linking group can have Structure 1L, synthesis of the O-acylimine compound, the C-diacyl com Structure 2L, Structure 3L, Structure 4L or Structure 5L. In pound and the primary amine are separate and independent Some embodiments, the linking group can have Structure 4L elements. Thus, in the second C-acylimine compound or Structure 5L. In other embodiments, the linking group can 60 description, the C-acylimine compound can be further have Structure 2L: alternatively, Structure 3L, alternatively, described using any combination of the C-diacyl compound Structure 4L; or alternatively, Structure 5L. element described herein and the primary amine element as described herein. As non-limiting examples, the C-acylimine C-Acylimine Compounds compound can be the O-acylimine compound product of The C-acylimine compounds can be described using any 65 contacting an O-diacyl compound with a primary amine one of several descriptions. While the O-acylimine com comprising an —NH group and an organyl group; alterna pound descriptions may be indicated by labels such as first tively, contacting an O-diacyl compound with a primary US 7,271,121 B2 27 28 amine comprising an —NH2 group and a metal salt com plexing group; alternatively, contacting an O-diacyl com TABLE 4-continued pound with a primary amine comprising an —NH2 group, a metal salt complexing group, and a linking group linking the Example C-Acylimine Compounds metal salt complexing group to the -NH group; alterna O tively, contacting an O-diacyl compound with a primary R13 N amine comprising an —NH group and an organyl group Rai1 N R 14 consisting of inert functional groups; alternatively, contact ing an O-diacyl compound with a primary amine comprising R11 (CH2) an —NH2 group and a hydrocarbyl group; alternatively, 10 R12 contacting an O-diacyl compound with a primary amine Structure 2b consisting of an —NH2 group and an organyl group; alter O natively, contacting an O-diacyl compound with a primary R13 amines consisting of an —NH group, a metal salt complex 15 Y N ing group, and a linking group linking the metal salt com Ral n R 15 plexing group to the -NH group; alternatively, contacting R11 an C-diacyl compound with a primary amine consisting of R 14 an —NH group and an organyl group consisting of inert Structure 3b functional groups; or alternatively, contacting an O-diacyl O compound with a primary amine consisting of an —NH R13 group and a hydrocarbyl group. The O-acylimine compound N can be further described using any combination of the Rai1 N R 14 C-diacyl compound element described herein and the pri R11 R 16 mary amine element as described herein. 25 In a third description, the O-acylimine compounds can be R12 R15 described as an O-acylimine compound product produced by Structure 4b any process as described herein and can be further described O using any embodiments of the processes as described herein. N R13 In a fourth description, the C-acylimine compound can be 30 Rai1 N R 14 described as having any structure as indicated in Table 4. In Some embodiments, the O-acylimine compound can have R11 R17 Structure 1b or Structure 27b; alternatively, Structure 2b or R12 R18 Structure 28b; alternatively, Structure 3b, Structure 4b, R 15 R 16 Structure 5b, Structure 29b, Structure 30b, or Structure 31b: 35 Structure Sb

alternatively, Structure 6b or Structure 32b; alternatively, Structure 7b, Structure 8b, mixtures of Structure 9b and Structure 10b, Structure 33b, Structure 34b, or mixtures of Structure 35b and Structure 36b; alternatively, Structure 11b, Structure 12b, Structure 13b, Structure 37b, Structure 40 38b, or Structure 39b; or alternatively, Structure 11b or Structure 37b. In other embodiments, the O-acylimine com pound can have Structure 27b; alternatively, Structure 28b; alternatively, Structure 29b, Structure 30b, or Structure 31b: R 16 alternatively, Structure 32b; alternatively, Structure 33b, 45 Structure 34b, or mixtures of Structure 35b and Structure 36b; alternatively, Structure 37b, Structure 38b, or Structure 39b; or alternatively, Structure 37b. In yet other embodi ments, the O-acylimine compound can have Structure 14b; alternatively, Structure 15b; alternatively, Structure 16b. 50 Structure 17b, or Structure 18b; alternatively, Structure 19b: alternatively, Structure 20b, Structure 21b, or mixtures of Structure 22b and Structure 23b; alternatively, Structure 24b, Structure 25b, or Structure 26b; or alternatively, Struc ture 24b. 55

TABLE 4 Example C-Acylimine Compounds R36 60

R35 R38 R37 65 Structure 8b US 7,271,121 B2 29 30

TABLE 4-continued TABLE 4-continued Example C-Acylimine Compounds Example C-Acylimine Compounds

O R40 Q L N R42 N Ral 1. n \ R13 O R 14 R3 I R43 10 R11 R3 9 R4 l (CH2) Structure 9b R12 Structure 15b

15 -L

O R42 N \ R13 O R3 I R43 R 15 R39 R41 R11 Structure 10b R 14 Structure 16b

25 Q-L N O \ R13 R 14 30 R11 R 16 R53 R55 R12 R 15 Structure 11b Structure 17b

O R52 35 -L N Ra I 1. n N

R I R56 40 R58 R53 R57 R55 Structure 12b 45 O R52 N R54 Ra I 1. n R 50

R53 R16 R' Structure 19b R55 R59 55 Structure 13b

oN O M R32 60

R31 R34 R33 Structure 14b 65 Structure 20b US 7,271,121 B2 31 32

TABLE 4-continued TABLE 4-continued Example C-Acylimine Compounds Example C-Acylimine Compounds

Q-L Q-L N R52 O \ R.32 O M R54 10 O R36 R R31 O C R56 R35 R38 R53 R60 15 R37 R55 R59 Structure 21b Structure 26b

Q-L Rall O l R4O Ra3 N O \ R42 n R2 R Ra13 Ra15 R3 I R43 25 Ral4 R39 R41 Structure 27b Structure 22b Rall Q 11 30 Ral M N O \ R40 Ra13 R3 I 35 Ral4 R42 Structure 28b R39 R41 R43 Rall O Structure 23b 13 40 Ra N R n R 15 R11 Ral3 Ra15 R 14

45 Ral4 Structure 29b

Rall O 13 Ral N R 50 S R 14 R R 16 Ra 13 Ra 15R12 R 15 Ral4 55 Structure 30b

Rall O 13 Ra3 N R 60 n R14 R11 R17 Ra13 Ra15 R12 R18 Ral4 R15 R16 Structure 25b 65 Structure 31b US 7,271,121 B2 33 34

TABLE 4-continued TABLE 4-continued Example C-Acylimine Compounds Example C-Acylimine Compounds Ra2

Rall Ra13 Ra2 10 Ra14 Ra13 Ra14 Structure 32b 15 Structure 37b

Ra2 Rall Ra2 Rall

O Ra13 N R32 N Ra13

Ra14 Ra15 R31 R34 Ra14

R33 25 Structure 33b

Ra2 Rall Structure 38b O 30 Ra13 N R32 Ra2 Rall

R36 O R52 Ra14 Ra15 R31 a3 R N R54 35 R35 R38 Ral4 R R56 R37 Structure 34b 40 R53 R60 Ra2 Rall R55 R59 O R40 Structure 39b Ra13 N R42 n 45 The C-acylimine compounds of Table 4 can be prepared utilizing various methods as described herein. Depending Ra14 Ra15 R31 R43 upon the C-acylimine compound preparation method, the R39 R41 C-diacyl compound and the primary amine can be separate Structure 35b and independent elements in the preparation of the 50 O-acylimine compound. Therefore, the R's of C-diacyl Ra13 compound having Structures 1-12 (Table 1), the R's of the Ra2 Ral4 primary amines having Structures 1a-4a, the linking groups 1L-5L (Table 3) of the primary amine having Structure 5a, 55 and the metal salt complexing group Rs having Structures Rall Ra15 1c-22c Table 2) of the primary amine having Structure 5a are separate and independent elements of the O-acylimine com N R40 pounds of Table 4. Thus, the O-acylimine compounds of O \ R42 Table 4 can be further described using any combination of 60 the R's of C-diacyl compound having Structures 1-12 (Table 1) as described herein, the R'S of the primary amines R31 R43 having Structures 1a-4a as described herein, the linking R39 R41 groups 1 L-5L (Table 3) of the primary amine having Struc Structure 36b 65 ture 5a as described herein, and the metal salt complexing group Rs having Structures 1c-22c (Table 2) of the primary amine having Structure 5a as described herein. US 7,271,121 B2 35 36 Metal Salts charges on X is equal to the oxidation state of M. In other The metal salts, M. X., employed in forming the embodiments, the total number of anions, p. is 2; or alter C-acylimine or C-diimine metal complexes can be any salt natively, 3. comprising any metal atom. Suitable metal salts can com In embodiments, tricoordinating metal salts can be chro prise any metal from groups IVB through VIII of the CAS mium(II) chloride, chromium(III) chloride, chromium(II) version of the periodic table of elements. In some embodi fluoride, chromium(III) fluoride, chromium (II) bromide, ments, the metal salt can be titanium, Zirconium, hafnium, chromium(III) bromide, chromium(II) iodide, chromium Vanadium, niobium, tantalum, chromium, manganese, iron, (III) iodide, chromium(II) acetate, chromium (III) acetate, cobalt, nickel, palladium, platinum, or mixtures thereof. In chromium(III) acetylacetonate, chromium(II) 2-ethylhex 10 anoate, chromium (II) triflate, chromium(III) nitrate, iron(II) other embodiments, the metal salt can comprise chromium, chloride, iron(III) chloride, iron(II) fluoride, iron(III) fluo iron, cobalt, nickel, palladium, or mixtures thereof, alterna ride, iron (II) bromide, iron(III) bromide, iron(II) iodide, tively, chromium, iron, cobalt, or mixtures thereof, alterna iron(II) iodide, iron(II) acetate, iron (III) acetate, iron(II) tively, iron, cobalt, or mixtures thereof; alternatively, nickel, acetylacetonate, iron(III) acetylacetonate, iron(II) 2-ethyl palladium, or mixtures thereof, alternatively, chromium; 15 hexanoate, iron (II) triflate, iron(III) nitrate, cobalt(II) chlo alternatively, iron; alternatively, cobalt; alternatively, nickel; ride, cobalt(III) chloride, cobalt(II) fluoride, cobalt(III) fluo or alternatively, palladium. ride, cobalt (II) bromide, cobalt(III) bromide, cobalt(II) In some embodiments, the metal salt is dicoordinating: iodide, cobalt(III) iodide, cobalt(II) acetate, cobalt (III) can complex with two complexing atoms (e.g. the two imine acetate, cobalt(II) acetylacetonate, cobalt(II) benzoylaceto nitrogen atoms of an O-diimine compound or the oxygen nate, cobalt(III) acetylacetonate, cobalt(II) 2-ethylhex atom of the acyl group and the nitrogen atom of the imine anoate, cobalt(II) triflate, cobalt(III) nitrate, vanadium (III) group of an O-acylimine compound). In other embodiments, chloride, vanadium (II) chloride, vanadium(III) chloride the metal salt can be tricoordinating; can complex with three tetrahydrofuran complex, Vanadium (III) iodide, manganese complexing atoms (e.g. the two imine nitrogen atoms and (II) acetate, manganese(II) acetylacetonate, manganese(II) heteroatom of the metal salt complexing group of an O-di 25 bromide, manganese(II) chloride, manganese(II) fluoride, imine compound). Typically, dicoordinating metal salts are manganese(III) fluoride, or manganese(II) iodide. In some utilized with bidentate C-diimine compounds and tricoordi embodiments, the tricoordinating metal salt can be chro nating metal salts are utilized with tridentate C-diimine mium(II) chloride, chromium(III) chloride, chromium(II) compounds. acetate, chromium (III) acetate, chromium(III) acetylaceto In some embodiments wherein the C-diimine compound 30 nate, iron(II) chloride, iron(III) chloride, iron(II) acetate, portion of the C-diimine metal complex is tridentate (e.g. the iron (III) acetate, iron(II) acetylacetonate, iron(III) acetylac C-diimine compound portion of the C-diimine metal com etonate, cobalt(II) chloride, cobalt(III) chloride, cobalt(II) plex comprises an O-diimine group and a metal salt com acetate, cobalt (III) acetate, or cobalt(II) acetylacetonate. In plexing group), the metal salt can comprise chromium, iron, other embodiments, the tricoordinating metal salt metal salt cobalt, or mixtures thereof; alternatively, iron, cobalt, or 35 can be chromium(II) chloride, chromium(III) acetylaceto mixtures thereof; alternatively, iron; or alternatively, cobalt. nate, iron(II) chloride, iron(II) acetylacetonate, iron(III) In Some embodiments wherein the C-diimine compound acetylacetonate, cobalt(II) chloride, cobalt(II) acetylaceto portion of the C-diimine metal complex is bidentate (e.g. the nate. In other embodiments, the tricoordinating metal salt C-diimine compound portion of the C-diimine metal com can be chromium(II) chloride; alternatively, chromium(III) plex comprises an O-diimine group and does not contain a 40 acetylacetonate; alternatively, iron(II) chloride; alterna metal salt complexing group), the metal salt can comprise tively, iron(II) acetylacetonate; alternatively, cobalt(II) chlo nickel, palladium, or mixtures thereof, alternatively, nickel, ride; or alternatively, cobalt(II) acetylacetonate. or alternatively, palladium. In embodiments, dicoordinating metal salts can be nickel (II) chloride, nickel(II) fluoride, nickel (II) bromide, nickel The anion X, of the metal salt can be any anion. In some 45 (II) iodide, nickel(II) acetate, nickel(II) acetylacetonate, embodiments, the anion X can be a halide, carboxylate, nickel(II) benzoylacetonate, nickel(II) 2-ethylhexanoate, acetonate, alkoxide, phenoxide, nitrate, Sulfate, phosphate, nickel (II) triflate, nickel(II) nitrate, palladium(II) chloride, or chlorate. In some embodiments, the anion, X, is a halide palladium(II) fluoride, palladium (II) bromide, palladium(II) or acetonate. In embodiments, the halide can be fluorine, iodide, palladium(II) acetate, palladium(II) acetylacetonate, chlorine, bromine, iodine, or combinations thereof, alterna 50 or palladium(II) nitrate. In some embodiments, the dicoor tively, chlorine, bromine, iodine, or combinations thereof. dinating metal salt can be nickel(II) chloride, nickel(II) alternatively, chlorine; alternatively, bromine, or alterna acetylacetonate, palladium(II) chloride, or palladium(II) tively, iodine. In carboxylate, acetonate, alkoxide or phe acetylacetonate. In other embodiments, the dicoordinating noxide embodiments, the carboxylate, acetonate, alkoxide, metal salt can be alternatively, nickel(II) chloride; alterna or phenoxide can be any C to Co carboxylate, acetonate, 55 tively, nickel(II) acetylacetonate; alternatively, palladium(II) alkoxide, or phenoxide; or alternatively, any C to Co chloride; or alternatively, or palladium(II) acetylacetonate. carboxylate, acetonate, alkoxide, or phenoxide. In some embodiments, the anion, X, can be a C to Co. acetonate: C-Acylimine Metal Complexes alternatively, a C to Co carboxylate; alternatively, a C to The C-acylimine metal complexes can be described using Co alkoxide; or alternatively, a C to Co phenoxide. In 60 any one of several descriptions. While the O-acylimine other embodiments, the anion X, can be acetylacetonate; metal complex descriptions may be indicated by labels such alternatively, acetate; alternatively, 2-ethylhexanoate; or as first description, second description, etc., these labels do alternatively, triflate. not indicate a particular preference to the description of the Generally, the number, p, of anions, X, is such that the C-acylimine metal complexes. total number of negative charges on the total number of X 65 In a first description, the O-acylimine metal complex can anions equals the oxidation state of M. In some embodi be described as a complex between an O-acylimine com ments, p is 1, 2, or 3, and the total number of negative pound and a metal salt. While this O-acylimine metal US 7,271,121 B2 37 38 complex description appears to imply a specific O-acylimine metal complex synthesis method, this is not the intent. The TABLE 5-continued method of preparing the C-acylimine metal complex is independent of the method of describing the O-acylimine Example C-Acylimine Metal Complexes metal complex. Thus, while the C-acylimine metal complex can be described as a complex between an O-acylimine compound and a metal salt, the O-acylimine metal complex can be prepared by contacting an O-acylimine compound Ra11 N and a metal salt or any other method described herein. The R15 C-acylimine compound and the metal salt are separate and 10 independent elements. Thus, the C-acylimine metal complex R11 can be further described using any combination of the R 14 C-acylimine compound element described herein and the Structure 3d metal salt element as described herein. 15 In a second description, the O-acylimine metal complex can be described as a product produced by any process described herein capable of producing the C-acylimine metal complex and can be further described using any embodiments of the processes described herein. In a third description, the C-acylimine metal complex can have any structure as indicated in Table 5. In some embodi ments, the C-acylimine metal complex can have Structure 1d or Structure 27d; alternatively, Structure 2d or Structure 28d; 25 alternatively, Structure 3d, Structure 4d, Structure 5d., Struc ture 29d, Structure 30d, or Structure 31d; alternatively, Structure 6d or Structure 32d; alternatively, Structure 7d, Structure 8d, mixtures of Structure 9d and Structure 10d, Structure 33d, Structure 34d, or mixtures of Structure 35d 30 and Structure 36d; alternatively, Structure 11d. Structure R1 5 RI 6 12d, Structure 13d, Structure 37d, Structure 38d, or Struc Structure 5d ture 39d; or alternatively, Structure 11d or Structure 37d. In other embodiments, the C-acylimine metal complex can have Structure 27d; alternatively, Structure 28d; alterna 35 tively, Structure 29d, Structure 30d, or Structure 31d; alter natively, Structure 32d; alternatively, Structure 33d, Struc ture 34d, or mixtures of Structure 35d and Structure 36d; alternatively, Structure 37d, Structure 38d, or Structure 39d: or alternatively, Structure 37d. In yet other embodiments, the 40 C-acylimine metal complex can have Structure 14d; alter natively, Structure 15d; alternatively, Structure 16d. Struc ture 17d, or Structure 18d; alternatively, Structure 19d; Structure 6d alternatively, Structure 20d, Structure 21d, or mixtures of Structure 22d and Structure 23d; alternatively, Structure 45 24d. Structure 25d, or Structure 26d; or alternatively, Struc ture 24d.

TABLE 5 50 Example C-Acylimine Metal Complexes R33 Structure 7d

55

60

65 Structure 8d US 7,271,121 B2 39 40

TABLE 5-continued TABLE 5-continued Example C-Acylimine Metal Complexes Example C-Acylimine Metal Complexes

X) - O R40 Q-L N \ R42 XM-N { \ R13 Ra11 CO 10 N R 14 R31 R43 R11 (CH2) R39 R41 Structure 9d Structure 15d

15

25

30 R12 R 15 Structure 17d

Q-L 35 XM-N d \ R13 N R 14 R 40 R17 2 R R18 R15 R16 Structure 18d

45

50

R16 R's

55

R55 R59 Structure 13d

g 60 p

O& R2 R31 R34 S’s 65 R1 R33 Structure 14d Structure 20d US 7,271,121 B2 41 42

TABLE 5-continued TABLE 5-continued Example C-Acylimine Metal Complexes Example C-Acylimine Metal Complexes g X. R52 O 10 N

15 R60

25

R39 R41 Structure 22d 30

35

40

45

50

55

60 Ral

Ra13 65 Ral4 Structure 25d Structure 31d US 7,271,121 B2 43 44

TABLE 5-continued TABLE 5-continued Example C-Acylimine Metal Complexes Example C-Acylimine Metal Complexes

Ra2

Ra13

10 Ra14

Structure 32d 15 Structure 37d Ra2 Rall Ra2 Rall XM-Q xy- R52 Ra13 K \ R32 R a3 N \ R54

Ra14 Ra15 R31 R34 Ra14 R R56

R33 25 Structure 33d R53 Ra12 Rall R55 XM-Q Structure 38d Ra13 N \ R32 30 Ra2 Rall xy- R52 R36 a3 Ra14 Ra15 R31 c R N \ R54 35 R35 R38 Ra14 R R37 Structure 34d O R56 R53 R60 40 Ra2 Rall R55 R59 y- R40 Structure 39d Ra13 N \ R42 The C-acylimine metal complexes of Table 5 can be 45 prepared utilizing various methods as described herein. Depending upon the C-acylimine metal complex preparation Ra14 Ra15 R31 R43 method, the C-diacyl compound, the primary amine, the R39 R41 metal salt, and/or the O-acylimine compound can each be Structure 35d separate and independent elements in the preparation of the 50 O-acylimine metal complex. Therefore, the R's of C-diacyl Ra13 compounds having Structures 1-12 (Table 1), the metal salts, the R's of the primary amines having Structures 1a–4a, the Ra2 Ral4 linking groups 1 L-5L (Table 3) of the primary amine having Structure 5a, and the metal salt complexing group R's 55 having Structures 1c-22c (Table 2) of the primary amine Rall Ra15 having Structure 5a are separate and independent elements of the O-acylimine metal complexes of Table 5. Thus, the XM-Np R40 O-acylimine metal complexes of Table 5 can be further O( \ R42 described using any combination of the R's of C-diacyl N 60 compounds having Structures 1-12 (Table 1) as described herein, the metal salts as described herein, the R's of the primary amines having Structures 1a-4a as described herein, R31 R43 the linking groups 1 L-5L (Table 3) of the primary amine R39 R41 having Structure 5a as described herein, and the metal salt Structure 36d 65 complexing group Rs having Structures 1c-22c (Table 2) of the primary amine having Structure 5a as described herein. US 7,271,121 B2 45 46 C.-Diimine Metal Complexes One aspect of the invention involves C.-diimine metal Structure 1g complexes. The C-diimine metal complexes can be Ra12 Rall described using any one of several descriptions. While the C-diimine metal complex descriptions may be indicated by labels such as first description, second description, etc., Ra13 these labels do not indicate a particular preference to the descriptions of the C-diimine metal complexes. Ra14 Ra15 In a first description, the C-diimine metal complex can be 10 described as a metal salt complexed to an O-diimine com pound or as a complex between a dimine compound and a In other embodiments, R' of Structures 1e to/through 13e metal salt, the C-diimine compounds. While these particular can have Structure 2 g (derived from a primary amine having C-diimine metal complex descriptions appear to imply a Structure 4a). specific C-diimine metal complex preparation method, this 15 is not the intent of C-diimine metal complex description. The Structure 2g method of preparing the C-diimine metal complex is inde Ra12 Rall' pendent of the method of describing the C-diimine metal complex. Thus, while the C-diimine metal complex may be described as a complex between an O-diimine compound and a metal salt, the C-diimine metal complex may be prepared by contacting an O-diimine compound and a metal Ral4 Ra15 salt, by contacting an O-acylimine compound, an amine and 25 a metal salt, or any other method described herein. The In other embodiments, R' of Structures 1e to/through 13e C-diimine compounds and metal salts are separate and can have Structure 1 g and R' of Structure 1e to/through independent elements of the C-diimine metal complex. Thus 13e can have Structure 2 g. In some embodiments, wherein within the first C.-diimine metal complex description, the R'' and R' of Structures 1e to/through 13e can have C-diimine metal complex can be described using any com 30 Structure 1 g and Structure 2 g, respectively, wherein bination of C-diimine compound as described herein and the Structure 1 g and Structure 2 g are different (not identical). metal salt as described herein. In some embodiments, the C-diimine metal complex can In embodiments, the C-diimine metal complex can be have Structure 14e or Structure 27e; alternatively, Structure 15e or Structure 28e; alternatively, Structure 16e, Structure described as a dicoordinate metal salt complexed to a 35 17e, Structure 18e, Structure 29e, Structure 30e, or Structure bidentate C-diimine compound. In some embodiments, the 31e; alternatively, Structure 19e or Structure 32e; alterna C-diimine metal complex can be described as a tricoordinate tively, Structure 20e, Structure 21e, mixtures of Structure metal salt complexed to a tridentate C-diimine compound. It 22e and Structure 23e. Structure 33e, Structure 34e, or should be noted that while the later embodiment describes mixtures of Structure 35e and Structure 36e; alternatively, the C-diimine metal complex as a tricoordinate metal salt 40 Structure 24e, Structure 25e, Structure 26e, Structure 37e, complexed to a tridentate C-diimine compound, this descrip Structure 38e, or Structure 39e; or alternatively, Structure tion does not necessarily imply that the three ligands of the 24e or Structure 37e. In other embodiments, the O-acylimine tridentate C-diimine compound are complexed to the metal compound can have Structure 14e; alternatively, Structure salt. For example, in example 7 a tricoordinate metal salt is 15e; alternatively, Structure 16e, Structure 17e, or Structure complexed to a tridentate C-diimine compound wherein the 45 18e; alternatively, Structure 19e; alternatively, Structure 20e, Structure 21e, or mixtures of Structure 22e and Struc metal salt complexing group is not complexed to the metal ture 23e; alternatively, Structure 24e, Structure 25e, or salt and can be utilized within other aspects of the invention Structure 26e; or alternatively, Structure 24e. In yet other as described herein. embodiments, the C-acylimine compound can have Struc In a second description, the C-diimine metal complex can 50 ture 27e; alternatively, Structure 28e; alternatively, Structure be described as a product produced by any process described 29e, Structure 30e, or Structure 31e; alternatively, Structure herein capable of producing the C-diimine metal complex 32e; alternatively, Structure 33e, Structure 34e, or mixtures and may be further described using any embodiments of the of Structure 35e and Structure 36e; alternatively, Structure processes described herein. 37e, Structure 38e, or Structure 39e; or alternatively, Struc In a third description, the C-diimine metal complex can be 55 ture 37e. described as having any structure as indicated in Table 6. In embodiments, the C-diimine metal complex can have Struc TABLE 6 ture le; alternatively, Structure 2e; alternatively, Structure Example C-Diimine Metal Complexes 3e, Structure 4e, or Structure 5e; alternatively, Structure 6e: 60 Ral' alternatively, Structure 7e, Structure 8e, or mixtures of M Structure 9e and Structure 10e; alternatively, Structure 11e. XM-N Structure 12e, or Structure 13e; or alternatively, Structure 11e. In some embodiments, R'' and R' of Structures Rai1 N R2 1e-13e are different (not identical). In some embodiments, 65 R' of Structures 1e to/through 13e can have Structure 1 g (derived from a primary amine having Structure 3a).

US 7,271,121 B2 49 50

TABLE 6-continued TABLE 6-continued

Example C-Diimine Metal Complexes Example C-Diimine Metal Complexes

R55 R59 Structure 13e g 1 \ XM-N Ra11 N R32 1 \ 's R31 R34 R 25 R33 Structure 14e Structure 20e

30

35

40

45

50

55

60

R41 R 15 R 6 R43 Structure 18e 65 Structure 23e US 7,271,121 B2 51 52

TABLE 6-continued TABLE 6-continued

Example C-Diimine Metal Complexes Example C-Diimine Metal Complexes

Q-L

Ra14 Structure 32e Structure 27e 55 Ra2 Rall Q o XM-N Ra13 ( \ R32 60 n

Ra14 Ra15 R R34 R33 Structure 28e 65 Structure 33e US 7,271,121 B2 53 54

TABLE 6-continued TABLE 6-continued

Example C-Diimine Metal Complexes Example C-Diimine Metal Complexes Ral2 Ra3 Rall Ra2 Rall x,y- Ra13 ( \ R32 10 n Ra14 Ra15 R31 c R36 15 R35 R38 R37 Structure 34e Ral2 Ra2 Rall g Ra3 Rall XM-N R40 Ra13 ( \ R42 25 R54 Ral 5 N n O R Ra14 Ra15 R31 R43 R56 R39 R41 30 Structure 35e R55 R59 Structure 39e

Ra12 Ra13 35 The C-diimine metal complexes of Table 6 can be pre pared utilizing various methods as described herein. Rall - Ra14 Depending upon the C-diimine metal complex preparation method the C-diacyl compound, the two primary amines, the -Mx N Ra15 40 LN / p R40 metal salt, the O-acylimine compounds, and/or the s N N \ R42 C-acylimine metal complexes can each be separate and independent elements in the preparation of the C-diimine metal complex. Therefore, the R's of C-diacyl compounds R31 R43 45 having Structures 1-12 (Table 1), the metal salts, the R's of R39 R41 the primary amines having Structures 1a-4a, the linking Structure 36e groups 1 L-5L (Table 3) of the primary amine having Struc ture 5a, and the metal salt complexing group Rs having Structures 1c-22c (Table 2) of the primary amine having 50 Structure 5a are separate and independent elements of the Ra12 C.-diimine metal complexes of Table 6. Thus, the C-diimine Ra3 Rall metal complexes of Table 6 can be further described using AN any combination of the R's of C-diacyl compound having XMp M 55 Structures 1-12 (Table 1) as described herein, the metal salts al4 N YN R \ | as described herein, the R's of the primary amines having Ra15 Structures 1a-4a as described herein, the linking groups 1L-5L (Table 3) of the primary amine having Structure 5a as R R52 described herein, and the metal salt complexing group R's 60 having Structures 1c-22c (Table 2) of the primary amine having Structure 5a as described herein. R53 R54 One skilled in the art will recognize that C-diimine metal R55 R56 complex Structures 14e though 39e formally show a mono Structure 37e 65 meric form of a tricoordinate metal salt complexed to a tridentate C.-diimine compound. However, it should be noted that these structures do not necessarily imply that dimeric US 7,271,121 B2 55 56 forms of Structures having bridging X groups are not In some embodiments, the two C-diimine nitrogen groups formed. Additionally, it should also be noted that while can be the same. In other embodiments, the two O-diimine C.-diimine metal complex Structures 14e though 39e, and nitrogen groups can be different. In particular embodiments, other Structures disclosed herein, indicate that the two imine the two O-diimine nitrogen groups comprise two different nitrogen and the metal salt complexing group form a dative 5 organyl groups; alternatively, comprise two different organyl bond with the metal atom, these structures do not necessarily groups consisting of inert functional groups; alternatively, imply that the three ligands of the tridentate C-diimine comprise two different hydrocarbyl groups; alternatively, compound are complexed to the metal salt. For example, in consist of two different organyl groups; alternatively, consist example 7 a tricoordinate metal salt is complexed to a of two different organyl groups consisting of inert functional tridentate C-diimine compound to form an O-diimine metal 10 groups; or alternatively, consist of two different hydrocarbyl complex isolated in a dimeric form and the metal salt groups. In some other particular embodiments, the first complexing group is not complexed to the metal salt. The C-diimine nitrogen group comprises an organyl group con examples further illustrate that this C.-diimine metal com sisting of inert functional groups and the second C-diimine plex of example 7 can be utilized within other aspects of the nitrogen group comprises a metal salt complexing group: invention as described herein. Provided the teachings of the 15 alternatively, the first C.-diimine nitrogen group comprises present disclosure, the skilled artisan may also recognize an organyl group consisting of inert functional groups and that the C-diimine metal complex Structures herein do not the second C-diimine nitrogen group comprises a metal salt show the presence of any complexing solvent molecules and complexing group and a linking group linking the metal salt may appreciate that depending upon the solvent(s) used in complexing group to second C-diimine nitrogen group nitro the preparation of C-diimine metal complex Structures le gen atom; alternatively, the first C-diimine nitrogen group though 39e, and other Structures disclosed herein, the C-di comprises a hydrocarbyl group and the second C-diimine imine metal complexes can be isolated in forms having nitrogen group comprises a metal salt complexing group: complexed solvent atoms, (e.g. THF, acetonitrile). alternatively, the first C-diimine nitrogen group comprises a hydrocarbyl group and the second C-diimine nitrogen group C.-Diimine Compounds 25 comprises a metal salt complexing group and a linking The C-diimine compounds can be described using any one group linking the metal salt complexing group to the second of several descriptions. While these descriptions may be C-diimine nitrogen group nitrogen atom; alternatively, the indicated by labels such first description, second description, first C-diimine nitrogen group consists of an organyl group etc., these labels do not indicate a preference towards a consisting of inert functional groups and the second C-di particular description of the C-diimine compounds. 30 imine nitrogen group consists of a metal salt complexing In a first description, the C-diimine compound can be group and a linking group linking the metal salt complexing minimally described as a compound comprising an O-di group to the second C-diimine nitrogen group nitrogenatom; imine group. In embodiments, the C-diimine compound can or alternatively, the first C.-diimine nitrogen group consists be described as a compound comprising 1) an O-diimine of a hydrocarbyl group and the second C-diimine nitrogen group and 2) two C-diimine nitrogen groups. In this first 35 group consists of a metal salt complexing group and a C-diimine compound description, the O-acylimine group can linking group linking the metal salt complexing group to the be further described as being derived from an O-diacyl second C-diimine nitrogen group nitrogen atom. compound. Thus, alternatively, the O-acylimine compound As the primary amine —NH group becomes the C-di can be described as compound comprising 1) an O-diimine imine group's nitrogen atom, the organyl group, metal salt group derived from an O-diacyl compound and 2) two 40 complexing group, linking group, organyl group consisting C-diimine nitrogen groups; or alternatively, as compound of inert functional groups, or hydrocarbyl groups of the consisting of 1) an O-diimine group derived from an O-dia primary amine becomes an O-diimine nitrogen group. Thus, cyl compound and 2) two C-diimine nitrogen group. In the the C-diimine nitrogen groups can have the same embodi first C.-diimine compound description, the C-diacyl com ments as the organyl group, metal Salt complexing group, pound, and each of the two C-diimine nitrogen groups are 45 linking group, organyl group consisting of inert functional separate and independent elements of the C-diimine com groups, and hydrocarbyl groups of the primary amine as pound description. Thus, within the first C.-diimine com described herein. Therefore, the organyl group, metal salt pound description, the C-diimine compound can have any complexing group, linking group, organyl group consisting combination of the C-diacyl compound as described herein of inert functional groups, and hydrocarbyl groups of the and the C-diimine nitrogen groups as described herein. 50 primary amines embodiment described herein are generally In the first C.-diimine compound description, the C-diacyl applicable to the description of the C-acylimine compound compound from which the C-diimine compound is derived with the proviso that the linking group links the metal salt can be any C.-diacyl compound described herein. In embodi complexing group to the imine nitrogen atom of the ments, the two C-diimine nitrogen groups can each inde O-acylimine group instead of the -NH group of the pri pendently comprise an organyl group; alternatively, com 55 mary amine. prise a metal salt complexing group; alternatively, comprise In a second description, the C-diimine compound can be a metal salt complexing group and a linking group linking described as an O-diimine compound product of contacting the metal salt complexing group to the C-diimine nitrogen an C-diacyl compound with two primary amines. While this group nitrogen atom; alternatively, comprise an organyl particular C-diimine compound description appears to imply group consisting of inert functional groups; alternatively, 60 a specific C-diimine compound synthesis method, this is not comprise a hydrocarbyl group; alternatively, consist of an the intent of C-diimine compound. The method of preparing organyl group; alternatively, consist of a metal salt com the C-diimine compound is independent of the description of plexing group and a linking group linking the metal salt the C-diimine metal complex. Thus, while the C-diimine complexing group to the C-diimine nitrogen group nitrogen compound can be described as an O-diimine compound atom; alternatively, consist of an organyl group consisting of 65 product of contacting an O-diacyl compound with two inert functional groups; or alternatively, consist of a hydro primary amines, the C-diimine compound can be prepared carbyl group. by using any method described herein. In the second C-di US 7,271,121 B2 57 58 imine compound description the C-diacyl compound and Structure 9f and Structure 10f, alternatively, Structure 11f. each of the two primary amines are separate and indepen Structure 12f, or Structure 13f, or alternatively, Structure dent elements of the C-diimine compound description. Thus, 11f. In some embodiments, R'' and R' of Structures 1f-13f within the second C-diimine compound description, the C-diimine compound can have any combination of the are different (not identical). In some embodiments, R' of C-diacyl compound as described herein and two primary Structures 1f-13f can have Structure 1 g (derived from a amines as described herein. primary amine having Structure 3a). In other embodiments, In the second C-diimine compound description, the C-dia R' of Structures 1 f-13f can have Structure 1 g can have cyl compound can be any C-diacyl compound described Structure 2 g (derived from a primary amine having Struc herein. In an aspect, the two primary amines are the same. 10 ture 4a). In other embodiments, Ra1 of Structures 1f-13f can In some embodiments, the two primary amines are different. have Structure 1 g and R' of Structures 1 f-13f can have In embodiments, at least one of the primary amines consists Structure 2 g. In yet other embodiments, wherein R'' and of an —NH group and a hydrocarbyl group or consists of R" of Structures 1f-13f can have Structure 1 g and Struc an —NH group and an organyl group consisting of inert ture 2 g, respectively, Structure 1 g and Structure 2 g are functional groups. In particular embodiments, the C-diimine 15 compound is a product of reacting an O-diacyl compound different (not identical). with two different the two primary amines comprising an In some embodiments, the C-diimine compound can have —NH, group and an organyl groups; alternatively, compris Structure 14f or Structure 27f, alternatively, Structure 15 for ing an —NH group and an organyl groups consisting of Structure 28f, alternatively, Structure 16f, Structure 17f. inert functional groups; alternatively, comprising an —NH Structure 18f, Structure 29f, Structure 30f, or Structure 31f. group and a hydrocarbyl group; alternatively, consisting of alternatively, Structure 19for Structure 32f; alternatively, an —NH group and an organyl groups; alternatively, con Structure 20f, Structure 21f, mixtures of Structure 22f and sisting of an —NH group and an organyl group consisting Structure 23f, Structure 33f, Structure 34f or mixtures of of inert functional groups; or alternatively, consisting of an Structure 35f and Structure 36f, alternatively, Structure 24f. —NH group and a hydrocarbyl group. 25 In embodiments, the C-diimine compound is a product of Structure 25f, Structure 26f, Structure 37f, Structure 38f, or reacting C-diacyl compound with two different primary Structure 39f, or alternatively, Structure 24 for Structure 37f. amines. In particular embodiments, the C-diimine com In other embodiments, the C-diimine compound can have pound is a product of reacting C-diacyl compound with two Structure 14f, alternatively, Structure 15f; alternatively, different primary amines, wherein the first primary amine 30 Structure 16f, Structure 17f, or Structure 18f alternatively, comprises an —NH group and an organyl group consisting Structure 19f; alternatively, Structure 20f Structure 21f, or of inert functional groups and the second primary amine mixtures of Structure 22f and Structure 23falternatively, comprises an —NH group and a metal salt complexing Structure 24f. Structure 25f, or Structure 26f, or alterna group; alternatively, the first primary amine comprises an tively, Structure 24f. In yet other embodiments, the C-di -NH group and an organyl group consisting of inert func 35 imine compound can have Structure 27f, alternatively, tional groups and the second primary amine comprises an —NH, group, a metal salt complexing group, and a linking Structure 28f, alternatively, Structure 29f, Structure 30f, or group linking the metal salt complexing group the —NH Structure 31f, alternatively, Structure 32f; alternatively, group; alternatively, the first primary amine comprises an Structure 33f, Structure 34f or mixtures of Structure 35f and -NH group and a hydrocarbyl group and the second 40 Structure 36f; alternatively, Structure 37f. Structure 38f, or primary amine comprises an —NH2 group and a metal salt Structure 39f, or alternatively, Structure 37f. complexing group; alternatively, the first primary amine comprises an —NH group and a hydrocarbyl group and the TABLE 7 second primary, amine comprises an —NH group, a metal salt complexing group, and a linking group linking the metal 45 Example C-Diimine Compounds salt complexing group to the —NH2 group; alternatively, the first primary amine consists of an —NH group and an organyl group consisting of inert functional groups and the second primary amine consists of an —NH group, a metal salt complexing group, and a linking group linking the metal 50 salt complexing group to the —NH group; or alternatively, the first primary amine consists of an —NH group and a hydrocarbyl group and the second primary amine consists of an —NH group, a metal salt complexing group, and a linking group linking the metal salt complexing group to the 55 —NH group. In a third description, the C-diimine compounds can be described as a product produced by any process described herein capable of producing the C-diimine compounds and may be further described using any embodiments of the 60 processes described herein. In a fourth description, the C-diimine compound can be R11 (CH2) described as having any a structure as indicated in Table 7. In embodiments, the C-diimine compound can have Struc R12 ture 1 f, alternatively, Structure 2f; alternatively, Structure 3f. 65 Structure 2f Structure 4f or Structure 5f; alternatively, Structure 6f. alternatively, Structure 7f, Structure 8f, or mixtures of US 7,271,121 B2 59 60

TABLE 7-continued TABLE 7-continued Example C-Diimine Compounds Example C-Diimine Compounds Ral' M Ral' N -N \ R13 N R40 Ra N R15 10 R11 R 14 Structure 3f R39 R41 Ral' Structure 9f M 15

13 Ral -N \ R Ral N R 14 \ R40 N \ 42 R11 R 16 R12 R 15 Structure 4f Ralf O c R R31 R43 Ral' R39 R41 M 25 N Structure 10f -N. \ R13 Ral N R 14 R R17 2 30 R R18 R 15 R 16 Structure 5f

Ral' R19 R20 35

Structure 11f

40

R16 R's Structure 6f Ral' 45

N R32

50

R3 3 Structure 7f

55

60

65 Structure 8f Structure 13f US 7,271,121 B2 61 62

TABLE 7-continued TABLE 7-continued

Example C-Diimine Compounds Example C-Diimine Compounds

Q-L oN N N \ R32 Ral N R2 10 R1 N

R R31 R34 Structure 14f R33 15 Structure 20f

oN N \ R32 Rai1 N R36 Structure 15f

25 R31 O Q-L R35 R38 R37 N \ R13 Structure 21f R1S 30 Q-L R11 R 15 R14 l R40 Structure 16f N \ R42 R1 N 35 R31 R43 oN N \ R13 R39 R41 R1 N R 14 Structure 22f 40 R11 R16 R12 R 15 Structure 17f

45

50

Structure 23f R 15 R 16

55 oN ryN, ) R52 60 R51 ( ) R54 R56 R16 R' R53 R55 Structure 19f 65 Structure 24f

US 7,271,121 B2 65 66

TABLE 7-continued TABLE 7-continued Example C-Diimine Compounds Example C-Diimine Compounds Ral2

Ra2 Rall Q Ra3 N R40 Ra13 N \ 10 Ral4

Ra14 Ra15 R31n O

R39 R41 15 Structure 35f

R55 R59 Ra12 Ra13 Structure 39f Ideally, the C-diimine compounds of Table 7 could be Rall Ra14 prepared from an O-diacyl compound and two primary amines which are separate and independent elements. Thus, Q als the R's of C-diacyl compound having Structures 1-12 (Table / \ So 25 1), the R's of the primary amines having Structures 1a4a, a. N R42 the linking groups 1 L-5L (Table 3) of the primary amine having Structure 5a, and the metal salt complexing group R’s having Structures 1c-22c (Table 2) of the primary R31 R43 amine having Structure 5a are separate and independent 30 elements of the C-diimine compounds of Table 7. Thus, the R39 R41 C.-diimine compounds of Table 7 can be further described Structure 36f using any combination of the R's of C-diacyl compounds having Structures 1-12 (Table 1) as described herein, the R's of the primary amines having Structures 1a4a as Ra12 35 described herein, the linking groups 1 L-5L (Table 3) of the primary amine having Structure 5a as described herein, and Ra3 Rall the metal salt complexing group Rs having Structures Q 1c-22c (Table 2) of the primary amine having Structure 5a ). as described herein. al4 N N 40 R \ General Metal Complex and Intermediate Synthesis Meth Ra15 ods An aspect of the invention relates to methods of preparing R C R52 C-diimine metal complexes. As described herein, production 45 of particular C-diimine metal complexes can motivate selec R53 R54 tion of particular starting materials, (e.g. C-diacyl com pounds, primary amines, and metal salts), intermediates (e.g. R55 R56 C-acylimine compounds and O-acylimine metal complexes), Structure 37f and C-diimine metal complexes. 50 The methods for producing an O-diimine metal complex generally comprise forming at least one imine bond in the presence of a metal salt, a metal complex, or combinations thereof and recovering an O-diimine metal complex. In some Ra3 embodiments, the method for producing an O-diimine metal 55 complex comprises forming at least one imine bond in the presence of a metal salt, C-acylimine metal complex, or Ral4 combinations thereof and recovering an O-diimine metal complex. In some embodiments, the method for producing an C-diimine metal complex comprises forming at least one 60 imine bond in the presence of a metal salt. In further embodiments, the method for producing an O-diimine metal complex comprises forming at least one imine bond in the presence of an O-acylimine metal complex. Within these methods, the metal salt or O-acylimine metal complex, the Structure 38f 65 C-diimine metal complex formed, and the specific imine bond or imine bonds formed, are separate and independent elements. Given the teachings provided, the skilled artisan US 7,271,121 B2 67 68 can recognize which combination of ingredients may lead to methods known to those skilled in the art, Such as recrys a desired C-diimine metal complex that includes the desired tallization. In yet other embodiments, the O-acylimine metal elements. The combinations of compounds that can be used complex can be used as is. to produce a particular C-diimine metal complex utilizing Within the first C.-acylimine metal complex production the synthesis methods are described herein. method the metal salt and O-acylimine compound are sepa The C-diacyl compounds, primary amines, and metal salts rate and independent elements. Thus, utilizing the first are separate and independent elements in the preparation of C-acylimine metal complex production method the the C-diimine metal complexes. Additionally, the interme C-acylimine metal complex can be prepared using any diate O-acylimine compounds and/or the C-acylimine metal combination of the metal salt as described herein and the complexes can be separate and independent elements of the 10 C-acylimine compound as described herein. In some C-diimine metal complex preparation methods. Thus, the embodiments, the O-acylimine compound can be a mixture C-diimine metal complex preparation methods can use any of similar O-acylimine compounds, e.g. a mixture of combination of the C-diacyl compounds described herein, C-acylimine compounds produced by contacting C-diacyl primary amines described herein, metal salts described compound with a mixture of primary amines consisting of herein, C-acylimine compounds described herein, and 15 an —NH2 group and a hydrocarbyl group, a mixture of C-acylimine metal complexes described herein to produce C-acylimine compounds produced by contacting C-diacyl the desired C-diimine metal complexes utilizing the herein compound with a mixture of primary amines consisting of described preparation methods. Provided the teachings of an —NH group and an organyl group consisting of inert the present disclosure, a skilled artisan should recognize functional groups, or a mixture of O-acylimine compounds how combinations of ingredients may be varied in order to produced by contacting an O-diacyl compound with a mix produce a desired metal complex including the desired ture of primary amines comprising an —NH group and an elements and their variations. metal salt complexing group. Methods for Preparing C-Acylimine Compounds In a second method, the method for preparing an The method of preparing an O-acylimine compound com C-acylimine metal complex comprises contacting an O-dia prises contacting an O-diacyl compound and a primary 25 cyl compound, a metal salt, and a primary amine. In some amine. In some embodiments, the C-acylimine compound is embodiments, an O-acylimine metal complex is recovered. recovered. In other embodiments, the C-acylimine com In other embodiments, the O-acylimine metal complex can pound can be purified using methods known to those skilled be purified using methods know to those skilled in the art, in the art, such as recrystallization. In yet other embodi Such as recrystallization. In yet other embodiments, the ments, the O-acylimine compound is used as is, e.g., as an 30 C-acylimine metal complex can be used as is. unpurified reaction product. In a third method, the method to produce an O-acylimine Within the O-acylimine compound production method the metal complex comprises a) contacting an C-diacyl com primary amine and the C-diacyl compound are separate and pound and a primary amine to form a mixture containing an independent elements. Thus, C-acylimine compound can be C-acylimine compound, and b) contacting a metal salt with prepared using any combination of the primary amine as 35 the mixture containing the C-acylimine compound. In some described herein and the C-diacyl compound as described embodiments, an O-acylimine metal complex is recovered. herein. In some embodiments, the primary amine can be a In other embodiments, the O-acylimine metal complex can mixture of similar primary amines, e.g. a mixture of primary be purified using methods known to those skilled in the art, amines consisting of an —NH group and hydrocarbyl Such as recrystallization. In yet other embodiments, the group, a mixture of primary amines consisting of an —NH 40 C-acylimine metal complex is used as is. group and an organyl group consisting of inert functional Within the second and third O-acylimine metal complex groups, or a mixture of primary amines comprising an production methods, the primary amine, the C-diacyl com —NH, group and a metal salt complexing group. In addi pound, and the metal salt are separate and independent tional embodiments, the C-diacyl compound can be a mix elements. Thus utilizing the second and third C-acylimine ture of C-diacyl compounds. 45 metal complex production methods, the C-acylimine metal Solvents and catalysts that can be utilized within the complex can be prepared utilizing any combination of the C-acylimine compound synthesis methods are described primary amine as described herein, the C-diacyl compound herein and are generally applicable to methods of producing as described herein, and the metal salt as described herein. C-acylimine compounds. Production conditions such as Provided the teachings of the present disclosure, a skilled reagent molar ratios, temperatures, pressure, and contact 50 artisan can recognize how combinations of ingredients, times, among others, are also described herein and are e.g.—a primary amine, C-diacyl compound, and metal salt, generally applicable to methods of producing O-acylimine may be varied in order to produce a desired metal complex compounds. including those ingredients and their variations. In some embodiments within the second and/or third O-acylimine Methods for Preparing C-Acylimine Metal Complexes 55 metal complex production methods, the primary amine can Various synthesis paths can be employed to produce the be a mixture of similar primary amines, e.g. a mixture of C-acylimine metal complexes. Described herein are several primary amines consisting of an —NH2 group and hydro preparation methods that can be utilized. While the carbyl group, a mixture of primary amines consisting of an C-acylimine metal complex preparation methods may be —NH group and an organyl group consisting of inert designated as first method, second method, etc . . . , these 60 functional groups, or a mixture of primary amines compris designations do not imply any preference for a particular ing an —NH group and a metal salt complexing group. In method of preparing the C-acylimine metal complexes. Some embodiments, within the second and third C-acylimine In a first method, the method of preparing an O-acylimine metal complex production methods, the C-diacyl compound metal complex comprises contacting an O-acylimine com can be a mixture of C-diacyl compounds. pound with a metal salt. In some embodiments, the 65 Solvent and catalysts and solvents that can be utilized C-acylimine metal complex is recovered. In other embodi within C-acylimine metal complex synthesis methods are ments, the C-acylimine metal complex can be purified using described herein and are generally applicable to methods of US 7,271,121 B2 69 70 producing O-acylimine metal complexes. Production condi consisting of an —NH group and an organyl group con tions such as reagent molar ratios, temperatures, pressure, sisting of inert functional groups, or a mixture of and contact times, among others, are also described herein C-acylimine compounds produced by contacting an O-diacyl and are generally applicable to methods of producing compound with a primary amine comprising an —NH C-acylimine metal complexes. group and an metal salt complexing group. In a second method, the method to produce an O-diimine Methods for Preparing Ol-Diimine Metal Complexes metal complex comprises a) contacting an O-acylimine Various synthesis paths can be employed to produce the compound, a metal salt, and a primary amine to form a C-diimine metal complexes by forming at least one imine mixture, and b) recovering the C-diimine metal complex bond in the presence of a metal salt, C-acylimine metal 10 from the mixture. In some embodiments, the C-diimine complex, or combinations thereof. Described herein are metal complex may be purified using methods known to several methods that can be utilized. While methods may be those skilled in the art, such as recrystallization. In yet other designated as first method, second method, etc., these embodiments, the C-acylimine metal complex can be used designations do not imply any preferences for particular as is, e.g., as an unpurified reaction product. method of preparing C-diimine metal complexes. 15 In a third method, the method to produce an O-diimine In a first method, the method to produce an O-diimine metal complex comprises a) contacting an O-acylimine metal complex, comprises a) contacting an O-acylimine compound and a metal salt to form a mixture containing an metal complex and a primary amine to form a mixture, and C-acylimine metal complex b) contacting a primary amine b) recovering the C-diimine metal complex from the mix with the mixture containing an O-acylimine metal complex ture. In some embodiments, the C-diimine metal complex and c) recovering the C-diimine metal complex. In some can be purified using methods known to those skilled in the embodiments, the C-diimine metal complex may be purified art, such as recrystallization. In yet other embodiments, the using methods known to those skilled in the art. Such as C-acylimine metal complex can be used as is. recrystallization. In yet other embodiments, the C-acylimine Within the first C.-diimine metal complex production metal complex can be used as is, e.g., as an unpurified method, the C-acylimine metal complex and the primary 25 reaction product. amine are separate and independent elements. Thus in the Within the second and third C-diimine metal complex first C-diimine metal complex production method, the C-di production methods, the C-acylimine compound, the metal imine metal complex can be prepared utilizing any combi salt, and the primary amine are separate and independent nation of O-acylimine metal complex as described herein elements. Thus within the second and third C-diimine metal and primary amine as described herein. In some particular 30 complex production methods, the C-diimine metal complex embodiments, the primary amine used to produce the can be produced using any combination of the C-acylimine O-acylimine compound of the O-acylimine metal complex compound as described herein, the metal salt as described and the primary amine contacted with the C-acylimine metal herein, and the primary amine as described herein. In some complex are different (not identical). For example, in two particular embodiments, the primary amine used to produce non-limiting examples, the primary amine can comprise an 35 the C-acylimine compound and the primary amine contacted —NH group and a metal salt complexing group and the with the O-acylimine compound are different (not identical). C-acylimine metal complex can comprise a complex For example, in two non-limiting examples, the primary between an O-acylimine compound and metal salt, wherein amine used to produce the O-acylimine compound can the C-acylimine compound comprises 1) an O-acylimine consist of an —NH2 group and a hydrocarbyl group and the group derived from an O-diacyl compound and 2) an imine 40 primary amine contacted with the C-acylimine compound nitrogen group consisting of a hydrocarbyl group; or the and metal salt or mixture containing an O-acylimine metal primary amine can consist of an —NH group and a hydro complex comprises an —NH group and metal salt com carbyl group and the O-acylimine metal complex can com plexing group; or the primary amine used to produce the prise a complex between an O-acylimine compound and C-acylimine compound consists of an —NH2 group and a metal salt wherein the O-acylimine compound comprises 1) 45 hydrocarbyl group and the primary amine contacted with the an O-acylimine group derived from an O-diacyl compound C-acylimine compound and metal salt or mixture containing and 2) an imine nitrogen group comprising a metal salt an O-acylimine metal complex consists of an —NH group complexing group. Provided the teachings of the present and hydrocarbyl group different than the primary amine disclosure, the skilled artisan should recognize how combi utilized to produce C-acylimine compound. Provided the nations of particular C-acylimine metal complexes and pri 50 teachings of the present disclosure, the skilled artisan should mary amines can be varied in order to produce an recognize how combinations of particular O-acylimine com C-acylimine metal complex that includes the C-acylimine pounds, metal salts, and primary amines can be varied in metal complex and primary amine selected. order to produce an O-acylimine metal complex including In some embodiments, the primary amine can be a mix the O-acylimine compound, metal salt, and primary amine ture of similar primary amines, e.g. a mixture of primary 55 selected. amines consisting of an —NH group and hydrocarbyl In some embodiments, the C-acylimine compound can be group, a mixture of primary amines consisting of an —NH a mixture of similar O-acylimine compounds, e.g. a mixture group and an organyl group consisting of inert functional of C-acylimine compounds produced by contacting C-diacyl groups, or a mixture of primary amines comprising an compound with a mixture of primary amine consisting of an —NH, group and a metal salt complexing group. In some 60 —NH group and a hydrocarbyl group, a mixture of embodiments, the C-acylimine metal complex can be a C-acylimine compounds produced by contacting C-diacyl mixture of similar O-acylimine metal complexes, e.g. a compound with a mixture of primary amine consisting of an mixture of C-acylimine compounds produced by contacting —NH group and an organyl group consisting of inert an C-diacyl compound with a mixture of primary amines functional groups, or a mixture of O-acylimine compounds consisting of an —NH group and a hydrocarbyl group, a 65 produced by contacting an O-diacyl compound with a mix mixture of C-acylimine compounds produced by contacting ture of primary amine comprising an —NH2 group and a an C-diacyl compound with a mixture of primary amines metal salt complexing group. In other embodiments, the US 7,271,121 B2 71 72 primary amine used in the synthesis of the C-diimine metal the art provided these teachings may also recognize that complex can be a mixture of similar primary amines, e.g. a even though the first, second, and third C-diimine metal mixture of primary amines consisting of an —NH group complex synthesis steps are annotated with stepsa), b), etc., and hydrocarbyl group, a mixture of primary amines con the C-diimine metal complex synthesis steps can be re sisting of an —NH group and an organyl group consisting annotated to provide consistent step annotation to incorpo of inert functional groups, or a mixture of primary amines rate steps utilized in producing the O-acylimine compounds comprising an —NH group and a metal salt complexing and/or the C-acylimine metal complexes into the C-diimine group. metal complex synthesis descriptions. Additionally, the act In some particular embodiments, the primary amine uti of incorporating the steps required to produce the lized in the first, second, and third C-diimine metal complex 10 C-acylimine compounds and/or O-acylimine metal com production methods described above is a different primary plexes into the methods of producing the C-diimine metal amine than that utilized to produce the C-acylimine com complexes can create a situation wherein a synthesis path pound or O-acylimine metal complex. For example in two may include more than one mixture. In these scenarios. Such non-limiting cases, if the primary amine used to produce mixtures can be prefaced with a descriptor Such as first, C-acylimine compound or C-acylimine metal complex com 15 second, etc., to provide unambiguous references to the prises an —NH group and an organyl group then the mixtures within the C-diimine metal complex synthesis. primary amine contacted with the O-acylimine compound or Thus, in a non limiting example, a process to produce an C-acylimine metal complex could be a different primary C-acylimine metal complex from an O-diacyl compound, amine comprising an —NH group and an organyl group; or, two primary amines, and a metal salt by putting together the if the primary amine used to produce O-acylimine compound various compound descriptions described herein can com or C-acylimine metal complex comprises an —NH group prise the steps a) contacting an O-diacyl compound with a and an organyl group consisting of inert functional groups, first primary amine to form a first mixture containing an then the primary amine contacted with the C-acylimine C-acylimine compound; b) contacting the first mixture with compound or O-acylimine metal complex could be primary a metal salt to form a second mixture containing an amines comprising an —NH group and a metal salt com 25 C-acylimine metal complex, c) contacting a second primary plexing group. One skilled in the art will recognize that these amine with the second mixture to form an O-diimine metal are non-limiting examples and can envision that within these complex, and d) recovering the C-diimine metal complex. embodiments any combination of the two primary amines as described herein can be utilized with the stipulation that the Reagent Molar Ratios, Solvents, Reaction Conditions and two primary amines are different. 30 Metal Complex and Intermediate Yields In a fourth method, the method to produce the C-diimine As described herein, an O-diimine metal complex may be metal complex comprises a) contacting an O-diimine com produced via various synthesis paths. Molar ratios of pound with a metal salt, and b) recovering the C-diimine reagents employed in the various synthesis paths are indi metal salt. In further embodiments, the C-diimine metal cated herein and can be generally applied to the methods of complex is purified using methods known to those skilled in 35 producing the C-diimine metal complex as described herein. the art, such as recrystallization. Within the fourth C-diimine Generally, whenever a primary amine is contacted with an metal complex production method, the C-diimine compound C-diacyl compound, e.g. to form an O-acylimine compound and metal salt are separate and independent elements. Thus, or an O-acylimine metal complex, the molar ratio of primary the C-diimine metal complex can be produced utilizing any amine to C-diacyl compound can be any molar ratio capable combination of the C-diimine compound as described herein 40 of producing the C-acylimine compound or O-acylimine and the metal salt as described herein. Provided the teach metal complex. In some embodiments, the molar ratio of ings of the present disclosure, the skilled artisan should primary amine to O-diacyl compound can be less than 1.1:1; recognize how combinations of C-diimine compound and alternatively, less than 1.05:1; alternatively, less than 1.02:1; metal salt may be varied in order to produce a particular or alternatively, less than 1:1. In other embodiments, the C-acylimine metal complex including the C-diimine com 45 molar ratio of primary amine to C-diacyl compound can pound and metal salt selected. range from 0.75:1 to 1.1:1; alternatively, range from 0.85:1 Applicable catalyst and solvent that can be utilized within to 1.05:1; or alternatively, range from 0.9:1 to 1.02:1. In yet these C-diimine metal complex synthesis methods are other embodiments, the molar ratio of primary amine to described herein and are generally applicable to methods of C.-diacyl compound can be about 1:1. In yet other embodi producing C-diimine metal complexes. Production condi 50 ments, the molar ratio of primary amine to O-diacyl com tions such as molar ratios, temperatures, pressure, and pound can be greater than 1:1 when the remaining acyl contact times, among others, are also described herein and group of the resultant C-acylimine compound does not are generally applicable to methods of producing C-diimine readily react with additional equivalents of the primary metal complexes. amine under the reaction conditions employed. In this The C-diimine metal complex synthesis method can also 55 embodiment, the use of excess primary amine can prove comprise any step required to produce the C-acylimine desirable. compounds and/or the C-acylimine metal complexes utilized Generally, whenever an O-diacyl compound is contacted in the C-diimine metal complex syntheses. As such, the with a metal salt, e.g. to form an O-acylimine metal complex C-diimine metal complex synthesis can be described as by contacting an O-diacyl compound, a primary amine, and process utilizing an O-diacyl compound, two primary 60 metal salt, the molar ratio of metal salt to C-diacyl com amines, and a metal salt and having an O-acylimine com pound can be any molar ratio capable of producing an pounds and/or O-acylimine metal complexes as an interme C-acylimine metal complex. In some embodiments, the diate product which can be isolated and/or purified or used molar ratio of metal salt to O-diacyl compound to is greater as is. Provided these C-diimine metal complex synthesis than 0.75:1; alternatively, greater than 0.85:1; alternatively, descriptions the skilled artisan may recognize that the two 65 greater than 0.9:1; or alternatively, greater than 0.95:1. In primary amines can be labeled first or second primary amine other embodiments, the molar ratio of metal salt to C-diacyl as needed to adequately describe the process. One skilled in compound can range from 0.75:1 to 1.25:1; alternatively, US 7,271,121 B2 73 74 range from 0.85:1 to 1.15:1; or alternatively, range from metal complex. In some embodiments, the molar ratio of 0.9:1 to 1.1:1. In yet other embodiments, the molar ratio of primary amine to metal salt to O-acylimine compound can metal salt to C-diacyl compound can be about 1:1. range from 0.75:1:1 to 1.1:1:1: alternatively, range from Generally, whenever primary amine is contacted with a 0.85:1:1 to 1.05:1:1; or alternatively, range from 0.9:1:1 to metal salt, e.g. to form an O-acylimine metal complex or an 1.02:1:1. In certain embodiments, the molar ratio of amine C-diimine metal complex, the molar ratio of primary amine to O-acylimine compound to metal salt can be about 1:1:1. to metal salt can be any molar ratio capable of producing the Generally, whenever a primary amine is contacted with an acylimine metal complex or the C-diimine metal complex. C-acylimine metal complex, e.g. to forman C-diimine metal In some embodiments, the molar ratio of primary amine to complex, the molar ratio of primary amine to O-acylimine metal salt can be less than 1.1:1; alternatively, less than 10 metal complex can be any primary amine to O-acylimine 1.05:1; alternatively, less than 1.02:1; or alternatively, less metal complex molar ratio capable of producing the C-di than 1:1. In yet other embodiments, molar ratio of amine to imine metal complex. In some embodiments, the molar ratio metal salt can range from 0.75:1 to 1:1, alternatively, range of primary amine to O-acylimine metal complex can be from 0.85:1 to 1.05:1; or alternatively, range from 0.9:1 to greater than 0.9:1; alternatively, greater than 0.95:1; or 1.02:1. In certain embodiments, the molar ratio of amine to 15 alternatively, greater than 0.975:1. In other embodiments, metal salt can be about 1:1. the molar ratio of primary amine to O-acylimine metal Generally, whenever an O-diacyl compound is contacted complex ranges from 0.9:1 to 1.5:1; alternatively, from with a primary amine and a metal salt, e.g. to form an 0.95:1 to 1:25:1; or alternatively, from 0.975:1 to 1.1:1. In C-acylimine metal complex, the molar ratio of the primary certain embodiments, the molar ratio of amine to amine to metal salt can be any molar ratio capable of C-acylimine metal complex is about 1:1. producing an O-acylimine metal complex. In some embodi Generally, the solvent for preparing the C-acylimine com ments, the molar ratio of primary amine to metal salt to pound, C-acylimine metal complex, or C-diimine metal C.-diacyl compound can range from 0.75:1:1 to 1.1:1:1: complex can be any solvent capable of allowing the selected alternatively, range from 0.85:1:1 to 1.05:1:1; or alterna reagents to react to form the selected compound or metal tively, range from 0.9:1:1 to 1.02:1:1. In certain embodi 25 complex. In embodiments, the solvent can be an alcohol, ments, the molar ratio of primary amine to metal salt to ether, nitrile or halogenated hydrocarbon. In some embodi C-diacyl compound is about 1:1:1. ments, the solvent can be an alcohol; alternatively, and ether; Generally, whenever an O-acylimine compound is con alternatively, a nitrile; or alternatively, a halogenated hydro tacted with a metal salt, e.g. to form an O-acylimine metal carbon. Generally, the alcohol, ether, nitrile, or halogenated complex or an O-diimine metal complex, the molar ratio of 30 hydrocarbon can be any C to Co alcohol, C to Coether, metal salt to C-acylimine compound can be any ratio capable C to Co nitrile or C to Co halogenated hydrocarbon; or of producing the C-acylimine metal complex or the C-di alternatively, any C to Cs alcohol, ether, C to Cs nitrile, or imine metal complex. In some embodiments, the molar ratio C to Cs halogenated hydrocarbon. In some embodiments, of metal salt to O-acylimine compound is greater than the alcohol solvent can be methanol, ethanol, propanol, 0.75:1; alternatively, greater than 0.85:1; alternatively, 35 isopropanol, butanol, or tert-butanol. In other embodiments, greater than 0.9:1; or alternatively, greater than 0.95:1. In the ether can be dimethyl ether, diethyl ether, methyl ethyl other embodiments, the molar ratio of metal salt to ether, monoethers or diethers of glycols (e.g. dimethyl O-acylimine compound ranges from 0.75:1 to 1.25:1; alter glycol ether), furans, dihydrofuran, substituted dihydro natively, ranges from 0.85:1 to 1.15:1; or alternatively, furans, tetrahydrofuran (THF), tetrahydropyrans, 1,3-diox ranges from 0.9:1 to 1.1:1. In yet other embodiments, the 40 anes, or 1,4-dioxanes. In other embodiments, the nitrile molar ratio of metal salt to C-acylimine compound is about solvent can be acetonitrile. In yet other embodiments, the 1:1. halogenated hydrocarbon can be methylene chloride, chlo Generally, whenever a primary amine is contacted with an roform, carbon tetrachloride, or 1,2-dichloroethane. In some C-acylimine compound, e.g. to form an O-diimine com particular embodiments, the solvent can be methanol; alter pound or an O-diimine metal complex, the molar ratio of 45 natively, ethanol; alternatively, isopropanol; alternatively, primary amine to O-acylimine compound is any primary tetrahydrofuran; alternatively, acetonitrile; alternatively, amine to O-acylimine compound molar ratio capable of methylene chloride; or alternatively, chloroform. producing the C-diimine compound or the C-diimine metal Generally, the formation of at least one imine bond of complex. In some embodiments, the molar ratio of primary C-diimine metal complex in the presence of a metal salt or amine to O-acylimine compound can be less than 1.25:1; 50 metal complex (e.g. reaction between a primary amine and alternatively, less than 1.15 to 1; or alternatively, less than C-acylimine metal complex or a reaction between a primary 1.1:1. The molar ratio of primary amine to O-acylimine amine, metal salt and an O-acylimine compound) can be compound can range from 0.75:1 to 1.25:1; alternatively, carried out at any suitable reaction conditions capable of range from 0.85:1 to 1.15:1; or alternatively, range from producing the C-diimine metal complex. For example, the 0.9:1 to 1.1:1. In certain embodiments, the molar ratio of 55 time, temperature, and/or pressure required to produce the primary amine to O-acylimine compound is about 1:1. In yet C-diimine metal complex by forming at least one imine bond other embodiments, the molar ratio of primary amine to of C-diimine metal complex in the presence of a metal salt C-diimine compound can be greater than 1:1 when the initial or metal complex can be any condition needed to produce a imine group is not readily displaced with the primary amine quantity of the O.-diimine metal complex. Provided the under the reaction conditions employed. In this embodiment, 60 teachings of the present disclosure, a skilled artisan may the use of excess primary amine can prove desirable. recognize the relationship between parameters, such as the Generally, whenever a primary amine, C-acylimine com temperature of the imine bond formation reaction and the pound, and a metal salt are contacted, e.g. to form an time necessary to form a quantity of the C-diimine metal C-diimine metal complex, the molar ratio of primary amine complex, and how to Suitably vary Such parameters. Addi to C-acylimine compound to metal salt to O-acylimine 65 tionally, provided the teachings of the present disclosure, the compound is any primary amine to metal salt to C-diacyl skilled artisan may also recognize that an imine bond compound molar ratio capable of producing the C-diimine formation reaction can also be dependent upon other reac US 7,271,121 B2 75 76 tion parameters such as molar ratio of reagents, and can vary it is believed that the reaction of the second amine with an the reaction parameters such as reagent mole ratio, reaction C-acylimine compound in the presence of a metal salt, or time, and/or reaction temperature to obtain desired results. reaction of the second amine with an O-acylimine metal Generally, the formation of at least one imine bond of complex, inhibits the reversibility of the Schiffbase reaction C-diimine metal complex in the presence of a metal salt or 5 that formed the first imine group of the C-acylimine com metal complex (e.g. reaction between a primary amine and pound. Normally, the reversibility of the Schiffbase reaction C-acylimine metal complex or a reaction between a primary does not create issues when the two primary amines used to amine, metal salt and an O-acylimine compound) can be produce the two imine group of the C-diimine compound carried out at any suitable reaction conditions capable of (and ultimately the C-diimine metal complex) are the same. producing the C-diimine metal complex. For example, the 10 However, when the two different primary amines are used to time, temperature, and/or pressure required to produce the produce two different imine nitrogen groups, the reversibil C-diimine metal complex by forming at least one imine bond ity of the Schiff base reaction allows the O-acylimine of C-diimine metal complex in the presence of a metal salt compound to revert into its component primary amine and or metal complex can be any condition needed to produce a C-diacyl compound and thus allows the formation of all quantity of the O.-diimine metal complex. Provided the 15 potential C-diimine compounds. Thus, the presence of the teachings of the present disclosure, a skilled artisan may metal salt or O-acylimine metal complex during the forma recognize the relationships between parameters, such as the tion of C-diimine metal complex allows improved selectiv temperature of the imine bond formation reaction and the ity to a specific desired C-diimine metal complex based upon time necessary to form a quantity of the C-diimine metal the limiting reagent of the synthesis method. complex, and how to Suitably vary Such parameters. Addi In embodiments, C.-diimine metal complex is produced at tionally, provided the teachings of the present disclosure, the an overall yield of greater than 50 percent based on the skilled artisan may also recognize that an imine bond weight of the limiting reagent; alternatively, greater than 55 formation reaction can also be dependent upon other reac percent based on the weight of the limiting reagent; alter tion parameters such as molar ratio of reagents, and can vary natively, the greater than about 60 percent based on the the reaction parameters such as reagent mole ratio, reaction 25 weight of the limiting reagent; alternatively, greater than 65 time, and/or reaction temperature to obtain desired results. percent based on the weight of the limiting reagent; alter In some embodiments, the reaction to form at least one natively, greater than 70 percent based on the weight of the imine bond of the C-diimine metal complex in the presence limiting reagent; alternatively, greater than 75 percent based of a metal salt or metal complex can occur at a temperature on the weight of the limiting reagent; or alternatively, greater ranging from -20°C. to 200°C. In other embodiments, the 30 than 80 percent based on the weight of the limiting reagent. reaction to form at least one imine bond of the C-diimine In some embodiments, the limiting reagent for determina metal complex in the presence of a metal salt or metal tion of the overall yield can be the C-diacyl compound. In complex can occur at a temperature ranging from 0° C. to other embodiments, the limiting reagent for determination of 150° C.; alternatively, from 20° C. to 100° C.; or alterna the overall yield is the can be the first primary amine. tively, from 40° C. to 80°C. The time needed to format least 35 Olefin Polymerization or Oligomerization one imine bond of resulting C-diimine metal complex in the The C-diimine metal complexes described in the present presence of a metal salt or metal complex, at the temperature application can be employed in the polymerization and/or described herein, may be from less than 1 minute to 48 oligomerization of olefins. Such a process can be carried out hours; alternatively, from 30 minutes to 36 hours; or alter by contacting a catalyst system comprising an O-diimine natively, from 1 hours to 24 hours. The temperatures and 40 metal complex with one or more olefin monomers under times described herein are generally applicable to any meth reaction conditions suitable for polymerization or oligomer ods of forming at least one imine bond in the presence of a ization of olefins. In some embodiments, the polymerization metal salt or metal complex including the methods for or oligomerization process comprises 1) contacting an ole contacting an O-diacyl compound, a metal salt and a primary fin, an O-diimine metal complex, and a cocatalyst, and 2) amine, contacting an O-acylimine compound, a metal salt, 45 forming an olefin polymer or oligomer. In other embodi and a primary amine, or contacting an O-acylimine metal ments, the polymerization or oligomerization process is an complex and a primary amine. alpha olefin production process comprising: 1) contacting In embodiments, the step wherein the imine bond of the ethylene, an O-diimine metal complex, and a cocatalyst; and C-diimine metal complex is formed in the presence of a 2) forming a product stream comprising alpha olefins. In metal salt or metal complex proceeds at a yield of greater 50 other embodiments, the polymerization or oligomerization than 60 percent based on the weight of the limiting reagent. process is an alpha olefin production process comprising: 1) In some embodiments, the step wherein the imine bond of contacting ethylene, an O-diimine metal complex, and a the C-diimine metal complex is formed in the presence of a cocatalyst; and 2) forming a product stream comprising metal salt or metal complex proceeds at a yield of greater polyethylene. The process can comprise additional steps than about 65 percent based on the weight of the limiting 55 Such as deactivating the catalyst and isolating the olefin reagent; alternatively, greater than 70 percent based on the oligomer or polymer. Suitable monomers for the olefin weight of the limiting reagent; alternatively, greater than 75 polymerization or oligomerization can be olefins having 2 to percent based on the weight of the limiting reagent; alter 20 carbon atoms; alternatively, olefins having 2 to 3 carbon natively, greater than 80 percent based on the weight of the atoms; alternatively, ethylene; or alternatively, propylene. limiting reagent; alternatively, greater than 85 percent based 60 on the weight of the limiting reagent; or alternatively, greater Olefin Polymerization or Oligomerization Catalysts and than 90 percent based on the weight of the limiting reagent. Cocatalysts Generally, the procedures described herein enable the Within the polymerization or oligomerization processes, production of specific C-diimine metal complexes having the C-diimine metal complex can be any C.-diimine metal two different (or two different type) imine groups in a high 65 complex described herein capable of forming the desired yield using an O-diacyl compound and two different (or two polymer or oligomer. In embodiments, the C-diimine metal different type) primary amines. Not to be bound by theory, complex can be a metal salt complexed to an O-diimine US 7,271,121 B2 77 78 compound comprising 1) an O-diimine group derived from second imine nitrogen group as described herein. Alterna an C-diacyl compound and 2) two different C.-diimine nitro tively, the C-diimine metal complexes utilized for the pro gen groups. In other non-limiting embodiments, the C-di duction of alpha olefins can be described using the alterna imine metal complex can be a metal salt complexed to an tive C-diimine metal complex descriptions equivalent to C-diimine compound comprising 1) an O-diimine group alpha olefin production C-diimine metal complexes indi derived from an O-diacyl compound and 2) two different cated herein. C-diimine nitrogen groups consisting of an organyl groups The metal salt of the C-diimine metal complex capable of consisting of inert functional groups, hydrocarbyl groups, or producing alpha olefins can be any metal salt as described mixture thereof, alternatively, a metal salt complexed to an herein. In embodiments, the metal salt can comprise iron, C-diimine compound consisting of 1) an O-diimine group 10 cobalt, or mixtures thereof. In some embodiments, the metal derived from an O-diacyl compound and 2) a first imine salt can comprise iron or cobalt. In some embodiments, the nitrogen group consisting of an organyl group consisting of metal salt can comprise iron; or alternatively, comprise inert functional groups or a hydrocarbyl group and 3) a cobalt. second imine nitrogen group comprising a metal salt com The C-diacyl compound from which the C-diimine group plexing group; or alternatively, a metal salt complexed to an 15 of the C-diimine metal complex capable of producing alpha C-diimine compound consisting of 1) an O-diimine group olefins is derived can be any C-diacyl compound as derived from an O-diacyl compound and 2) a first imine described herein. In embodiments, the C-diimine group can nitrogen group consisting an organyl group consisting of be derived from an aromatic C-diacyl compound. In some inert functional groups or a hydrocarbyl group and 3) a embodiments, the C-diimine group of the C-diimine metal second imine group comprising a metal salt complexing complex can be derived from acenaphthenequinone, a Sub group and a linking group linking the metal salt complexing stituted acenaphthenequinone, phenanthrenequinone, a Sub group to the second imine nitrogen atom. As the metal salt, stituted phenanthrenequinone, pyrenequinone, or a substi C-diacyl compound from which the C-diimine compound is tuted pyrenequinone. In other embodiments, the C-diimine derived, and the two imine groups originate from indepen group of the C-diimine metal complex can be derived from dent elements, the C-diimine metal complex utilized to 25 acenaphthenequinone, phenanthrenequinone, or pyrene polymerize or oligomerize olefins can be further described quinone. In yet other embodiments, the C-diimine group of using any combination of the metal salt as described herein, the C-diimine metal complex can be derived from acenaph the C-diacyl compound from which the C-diimine com thenequinone; alternatively, phenanthrenequinone; or alter pound is derived as described herein, any first imine nitrogen natively, pyrenequinone. group as described herein, any second imine nitrogen group 30 The first imine nitrogen group within the C-diimine group metal salt complexing group as described herein, and any of some C-diimine metal complexes capable of producing linking group linking the metal salt complexing group to the alpha olefins can be any organyl group consisting of inert of the second imine nitrogen group as described herein. functional groups or a hydrocarbyl group as described Alternatively, the C-diimine metal complexes utilized for the herein. In an aspect, the organyl group consisting of inert polymerization or oligomerization of olefins can be 35 functional groups of the first imine nitrogen group can described using the alternative C-diimine metal complex consist of a phenyl group or a Substituted phenyl group descriptions equivalent to the polymerization or oligomer (Substituted phenyl group consisting of inert functional ization C-diimine metal complexes indicated herein. groups). In embodiments, the hydrocarbyl group of the first The process to produce alpha olefins can utilize any imine nitrogen group can consist of a phenyl group or a C-diimine metal complex capable of producing alpha ole 40 Substituted phenyl group. In some embodiments, the hydro fins. In non-limiting embodiments, the C-diimine metal carbyl group of the first imine nitrogen group can be a complex capable of producing alpha olefins can be a metal 2-substituted phenyl group; alternatively, a 2,6-disubsituted salt complexed to an O-diimine compound comprising 1) an phenyl group; or alternatively, a 2,4,6-trisubstituted phenyl C-diimine group derived from an O-diacyl compound and 2) group. In other embodiments, the hydrocarbyl group of the a first imine nitrogen group consisting of an organyl group 45 first imine nitrogen group can be a 2,6-dimethylphenyl consisting of inert functional groups or a hydrocarbyl group group, a 2,6-diethylphenyl group, a 2,6-diisopropylphenyl and 3) a secondimine nitrogen group comprising a metal salt group, or a 2,6-di-tert-butylphenyl group. In yet other complexing group and a linking group linking the metal salt embodiments, the hydrocarbyl group of the first imine complexing group to the second imine nitrogen atom; or nitrogen group can be a 2,6-dimethylphenyl group, a 2.6- alternatively, a metal salt complexed to an O-diimine com 50 diethylphenyl group, or a 2,6-diisopropylphenyl group. In pound consisting of 1) an O-diimine group derived from an further embodiments, the hydrocarbyl group of the first C-diacyl compound and 2) a first imine nitrogen group imine nitrogen group can be a 2,6-dimethylphenyl group; consisting of an organyl group consisting of inert functional alternatively, a 2,6-diethylphenyl group; alternatively, a 2.6- groups or a hydrocarbyl group and 3) a second imine diisopropylphenyl group; alternatively, a 2,6-di-tert-bu nitrogen group consisting of a metal salt complexing group 55 tylphenyl group; or alternatively, a 2.4.6-trimethylphenyl and a linking group linking the metal salt complexing group group (mesityl group). to the second imine nitrogen atom. As the metal salt, Particular combinations of the metal salt complexing C-diacyl compound from which the C-diimine compound is group and linking group linking the metal salt complexing derived, and the two imine groups originate from indepen group to the second imine nitrogen atom within the C-di dent elements, the C-diimine metal complex capable of 60 imine compound of the C-diimine metal complex can be producing alpha olefins can be further described using any advantageous for producing alpha olefins. In aspects, the combination of the metal salt as described herein, the second imine group can comprise a dialkyl aminyl group, a C-diacyl compound from which the C-diimine compound is diphenyl aminyl group, a Substituted diphenyl aminyl group derived as described herein, any first imine nitrogen group a dialkyl phosphinyl group, a diphenyl phosphinyl group, or as described herein, any second imine nitrogen group metal 65 a Substituted diphenyl phosphinyl group and —(CH2) - salt complexing group as described herein, and any linking linking group where m is 2 or 3; alternatively, can comprise group linking the metal salt complexing group to the of the a pyridinyl group, a Substituted pyridinyl group, a furanyl US 7,271,121 B2 79 80 group, a Substituted furanyl group, a thiophenyl group, or a Sulfidyl group, or a Substituted phenyl sulfidyl group and a Substituted thiophenyl group and a —(CH)— linking —(CHCH)— linking group. Alternatively, the second group; or alternatively, can comprise an alkyl etheryl group, imine nitrogen group can consist of a dialkyl aminyl group, a phenyl etheryl group, a Substituted phenyl etheryl group, a diphenyl aminyl group, a dialkyl phosphinyl group, or a an alkyl Sulfidyl group, a phenyl sulfidyl group, or a Sub diphenyl phosphinyl group and a —(CH2)—linking group stituted phenyl sulfidyl group and a —(CH2CH)—linking where m is 2 or 3; alternatively, can consist of a pyridinyl group. Alternatively, the second imine nitrogen group can group, a furanyl group, or a thiophenyl group and a comprise a dialkyl aminyl group, a diphenyl aminyl group, —(CH2)— linking group; alternatively, can consist of an a dialkyl phosphinyl group, or a diphenyl phosphinyl group alkyl etheryl group or an alkyl sulfidyl group and a and a —(CH), linking group where m is 2 or 3: 10 —(CH2CH2)— linking group; or alternatively, can consist alternatively, can comprise a pyridinyl group, a furanyl of a phenyl etheryl group or an phenyl sulfidyl group and a group, or a thiophenyl group and a —(CH2)— linking —(CH2CH2)— linking group. In some embodiments, the group; alternatively, can comprise an alkyl etheryl group or second imine group can consist of a diphenyl aminyl group, an alkyl sulfidyl group and a —(CHCH)—linking group: a Substituted diphenyl aminyl group, a diphenyl phosphinyl or alternatively, can comprise a phenyl etheryl group or an 15 group, or Substituted a diphenyl phosphinyl group and a phenyl sulfidyl group and a —(CH2CH)—linking group. —(CH), linking group where m is 2 or 3; alternatively, In some embodiments, the secondimine group can comprise can consist of a diphenyl aminyl group or a diphenyl a diphenyl aminyl group, a Substituted diphenyl aminyl phosphinyl group and a —(CH2) -linking group where m group, a diphenyl phosphinyl group, or Substituted a diphe is 2 or 3; alternatively, can consist of a substituted diphenyl nyl phosphinyl group and a —(CH) - linking group aminyl group, or a substituted diphenyl phosphinyl group where m is 2 or 3; alternatively, can comprise a diphenyl and a —(CH), linking group where m is 2 or 3: aminyl group or a diphenyl phosphinyl group and a alternatively, can consist of a diphenyl phosphinyl group or —(CH), linking group where m is 2 or 3; alternatively, a substituted diphenyl phosphinyl group and a —(CH) - can comprise a Substituted diphenyl aminyl group, or a linking group where m is 2 or 3; alternatively, can consist of Substituted diphenyl phosphinyl group and a —(CH) - 25 a diphenyl phosphinyl group and a —(CH) - linking linking group where m is 2 or 3; alternatively, can comprise group where m is 2 or 3; alternatively, can consist of a a diphenyl phosphinyl group or a Substituted diphenyl Substituted diphenyl phosphinyl group and a —(CH) - phosphinyl group and a —(CH) -linking group where m linking group where m is 2 or 3; alternatively, can consist of is 2 or 3; alternatively, can comprise a diphenyl phosphinyl a diphenyl phosphinyl group or a Substituted diphenyl group and a —(CH), linking group where m is 2 or 3: 30 phosphinyl group and a —(CHCH)—linking group; alter alternatively, can comprise a substituted diphenyl phosphi natively, can consist of a diphenyl phosphinyl group and a nyl group and a —(CH), linking group where m is 2 or —(CHCH)—linking group; alternatively, can consist of a 3; alternatively, can comprise a diphenyl phosphinyl group Substituted diphenyl phosphinyl group and a —(CHCH)— or a Substituted diphenyl phosphinyl group and a linking group; alternatively, can consist of a 2-pyridinyl —(CHCH)—linking group; alternatively, can comprise a 35 group or a substituted 2-pyridinyl group and a —(CH)— diphenyl phosphinyl group and a —(CH2CH2)— linking linking group; alternatively, a 2-pyridinyl group and a group; alternatively, can comprise a Substituted diphenyl —(CH)—linking group; alternatively, a Substituted 2-py phosphinyl group and a —(CH2CH)—linking group; alter ridinyl group and a —(CH)—linking group; alternatively, natively, can comprise a 2-pyridinyl group or a substituted can consist of a phenyl etheryl group, a Substituted phenyl 2-pyridinyl group and a —(CH)—linking group; alterna 40 etheryl group, a phenyl sulfidyl group, or a Substituted tively, a 2-pyridinyl group and a —(CH)—linking group; phenyl Sulfidyl group and a —(CH2CH2)— linking group; alternatively, a Substituted 2-pyridinyl group and a alternatively, can consist of a phenyl etheryl group, or a —(CH2)— linking group; alternatively, can comprise a phenyl Sulfidyl group and a —(CH2CH2)— linking group; phenyl etheryl group, a Substituted phenyl etheryl group, a alternatively, can consist of a substituted phenyl etheryl phenyl sulfidyl group, or a Substituted phenyl sulfidyl group 45 group, or a Substituted phenyl Sulfidyl group and a and a —(CH2CH)—linking group; alternatively, can com —(CH2CH2)—linking group; alternatively, can consist of a prise a phenyl etheryl group, or a phenyl sulfidyl group and phenyl sulfidyl group or a substituted phenyl Sulfidyl group a —(CH2CH2)—linking group; alternatively, can comprise and a —(CH2CH)—linking group; alternatively, can con a Substituted phenyl etheryl group, or a substituted phenyl sist of a phenyl sulfidyl group and a —(CHCH)—linking Sulfidyl group and a —(CH2CH)—linking group; alterna 50 group; or alternatively, can consist of a Substituted phenyl tively, can comprise a phenyl sulfidyl group or a substituted Sulfidyl group and a —(CH2CH)—linking group. phenyl Sulfidyl group and a —(CH2CH)—linking group; In a non-limiting aspect, the Odiimine metal complex alternatively, can comprise a phenyl Sulfidyl group and a capable of producing alpha olefins can comprise a metal salt —(CHCH)—linking group; or alternatively, can comprise comprising iron complexed to an O-diimine compound a Substituted phenyl Sulfidyl group and a —(CH2CH2)— 55 comprising 1) an O-diimine group derived from aromatic linking group. dione; 2) a first imine nitrogen group consisting of a 2.6- In other aspects, the second imine group can consist of a disubstituted phenyl group; and 3) a second imine nitrogen dialkylaminyl group, a diphenyl aminyl group, a Substituted group comprising a metal salt complexing group and a diphenyl aminyl group a dialkyl phosphinyl group, a diphe linking group linking the metal salt complexing group to the nyl phosphinyl group, or a Substituted diphenyl phosphinyl 60 second imine nitrogen atom; or alternatively, a metal salt group and —(CH), linking group where m is 2 or 3: comprising iron complexed to an O-diimine compound alternatively, can consist of a pyridinyl group, a Substituted comprising 1) an O-diimine group derived from aromatic pyridinyl group, a furanyl group, a Substituted furanyl dione; 2) a first imine nitrogen group consisting of a 2.6- group, a thiophenyl group, or a substituted thiophenyl group disubstituted phenyl group; and 3) a second imine nitrogen and a —(CH)—linking group; or alternatively, can consist 65 group consisting of a metal salt complexing group and a of an alkyl etheryl group, a phenyl etheryl group, a Substi linking group linking the metal salt complexing group to the tuted phenyl etheryl group, an alkyl sulfidyl group, a phenyl second imine nitrogen atom. In some non-limiting embodi US 7,271,121 B2 81 82 ments, the C-diimine metal complex capable of producing Alternatively, the cocatalyst can be mixed with the olefin alpha olefins can comprise a metal salt comprising iron and/or the solvent prior to contact with the C-diimine metal complexed to an O-diimine compound comprising 1) an complex. C-diimine group derived from acenaphthenequinone, phenanthrenequinone, or pyrenequinone; 2) a first imine Polymerization or Oligomerization Solvents, Reactors, nitrogen group consisting of a 2,6-dimethylphenyl group, a Reaction Conditions and Products 2,6-diethylphenyl group, or a 2,6-dilsopropylphenyl group; In embodiments, the polymerization or oligomerization and 3) a secondimine nitrogen group comprising a metal salt reaction can occur in a solvent or diluent. In some embodi complexing group and a linking group linking the metal salt ments, the solvent or diluent can comprise a C, to Cao complexing group to the second imine nitrogen atom. In 10 hydrocarbon; or alternatively, a C to Co. hydrocarbon. The other non-limiting embodiments, the C-diimine metal com hydrocarbon solvent can be a Saturated hydrocarbon, an plex capable of producing alpha olefins can comprise a aromatic hydrocarbon or an olefinic hydrocarbon. In some metal salt comprising iron complexed to an O-diimine embodiments, the saturated hydrocarbon solvent can be a Ca compound comprising 1) an O-diimine group derived from to Co Saturated hydrocarbon. In other embodiments, the acenaphthenequinone, phenanthrenequinone, or pyrene 15 saturated solvent can be butane, isobutane, hexane, heptane, quinone; 2) a first imine nitrogen group consisting of a cyclohexane, or mixtures thereof. In some embodiments, the 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, or a aromatic solvent can be a C to Co aromatic compound. In 2,6-dilsopropylphenyl group; and 3) a secondimine nitrogen Some embodiments, the aromatic solvent can be benzene, group consisting of a metal salt complexing group and a toluene, xylene(s), ethylbenzene, or mixtures thereof. In linking group linking the metal salt complexing group to the other embodiments, another embodiment, the olefinic second imine nitrogen atom. Further embodiments of the hydrocarbon solvent can comprise alpha olefins. In other elements of the C-diimine metal complex capable of pro embodiments, the alpha olefin solvent comprises a C to Co ducing alpha olefins are described herein. alpha olefin; alternatively, a C to C2 alpha olefin; alterna Generally, the cocatalyst can be any organometallic com tively, alternatively, a C to Cs alpha olefin. In yet other pound capable of activating the C-diimine metal complex to 25 embodiments, the alpha olefin solvent can be 1-butene, polymerize or oligomerize olefins. Suitable cocatalysts can 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or include monomeric or oligomeric metal alkyls, metal aryls, combinations thereof. metal alkyl-aryls comprising at least one of the metals Unless specified otherwise, the terms contacted, com selected from the group consisting of B, Al, Be, Mg, Ca, Sr. bined, and “in the presence of refer to any addition Ba, Li, Na, K, Rb, Cs, Zn, Cd, and Sn. In embodiments, the 30 sequence, order, or concentration for contacting or combin cocatalyst can be selected from the group consisting of ing two or more components of the polymerization reaction. organoaluminum compounds, organoboron compounds, Combining or contacting of polymerization or oligomeriza organolithium compounds, or mixtures thereof. In some tion components, according to the various methods embodiments, the cocatalyst can be an organoaluminum described herein may occur in one or more contact Zones compound. Applicable organoaluminum compounds can 35 under Suitable contact conditions such as temperature, pres include trialkylaluminums, alkylaluminum halides, alumox Sure, contact time, flow rates, etc . . . . The contact Zone can anes or mixture thereof. In some embodiments, the orga be disposed in a vessel, e.g. a storage tank, tote, container, noaluminum compound can be trimethylaluminum triethy mixing vessel, reactor, etc.; a length of pipe, e.g. a tee, inlet, laluminum, diethylaluminum chloride, diethylaluminum injection port, or header for combining component feed lines ethoxide, diethylaluminum cyanide, diisobutylaluminum 40 into a common line; or any other Suitable apparatus for chloride, triisobutylaluminum, ethylaluminum sesquichlo bringing the components into contact. The methods may be ride, methylalumoxane (MAO), modified methylalumoxane carried out in a batch or continuous process as is suitable for (MMAO), isobutyl alumoxanes, t-butyl alumoxanes, or mix a given embodiment, with physical parameters of the contact tures thereof. In other embodiments, the organoaluminum Zone being specified accordingly. compounds can include methylalumoxane (MAO), modified 45 In embodiments, the polymerization or oligomerization methylalumoxane (MMAO), isobutyl alumoxanes, t-butyl can be a continuous process carried out in one or more alumoxanes, or mixtures thereof. In other embodiments, the reactors. In some embodiments, the continuous polymeriza cocatalyst can be methylalumoxane, modified methylalu tion or oligomerization process reactor can comprise a loop moxane, or mixtures thereof. In yet other embodiments, the reactor, a tubular reactor, a continuous stirred tank reactor cocatalyst can be methylalumoxane; alternatively, modified 50 (CSTR), or combinations thereof. In other embodiments, the methylalumoxane: isobutylalumoxane (IBAO); or alterna continuous polymerization or oligomerization process reac tively, partially hydrolyzed trialkylaluminum. tor can be a loop reactor; alternatively, a tubular reactor; or In embodiments, the molar ratio of the metal of the alternatively, a continuous stirred tank reactor (CSTR). In cocatalyst to the metal of the C-diimine metal complex can other embodiments, the continuous polymerization or oli range from 1:1 to 10,000:1; alternatively, from 10:1 to 55 gomerization process reactor can be employed in the form of 5,000:1; or alternatively, from 100:1 to 3,000:1; or alterna different types of continuous reactors in combination, and in tively, from 200:1 to 2,000:1. In embodiments wherein the various arrangements. In an embodiment, the continuous C-diimine metal complex comprises a iron salt and the reactor can be a combination of a tubular reactor and a cocatalyst is an alumoxane the molar ratio of aluminum to CSTR. In other embodiments, the continuous polymeriza iron can range from 1:1 to 10,000:1; alternatively, from 10:1 60 tion or oligomerization process reactor can be two or more to 5,000:1; alternatively, from 100:1 to 3,000:1; or alterna reactors in series, two or more reactors in parallel, or tively, from 200:1 to 2,000:1. combinations thereof. In an embodiment, the continuous The C-diimine metal complex, cocatalyst(s), and olefin polymerization or oligomerization process reactor can be can be contacted in any manner known to those skilled in the more than one CSTR in series. In another embodiment, the art. For instance, the C-diimine metal complex and the 65 continuous reactor can be a tubular reactor and a loop reactor cocatalyst can be mixed first before bringing into contact in series. In yet another embodiment, the continuous reactor with a feed comprising an olefin or an olefin mixture. can be two or more loop reactors in series. US 7,271,121 B2 83 84 Suitable polymerization or oligomerization reaction con tion pressure can be allowed to decrease without adding any ditions such as temperatures, pressures and times can be additional gaseous monomer and/or inert gas. impacted by a number of factors such as C-diimine metal The reaction time of the polymerization or oligomeriza complex identity, C.-diimine metal complex stability, C.-di tion reaction can be any reaction time required to produce imine metal complex activity, cocatalyst identity, cocatalyst the desired quantity of polymerization or oligomerization activity, desired product (e.g. polyethylene versus alpha product (Such as polyethylene or alpha olefins), obtain a olefins), desired product distribution, and/or desired product desired catalyst productivity, and/or obtain a desired con purity among others. Provided the teachings of the present version of monomer. In some embodiments, the polymer disclosure, one skilled in the art will recognize how to adjust ization or oligomerization reaction time ranges from 1 the polymerization or oligomerization reaction conditions to 10 minute to 5 hours; alternatively, ranges from 5 minutes to 2.5 hours; alternatively, ranges from 10 minutes to 2 hours; or achieve the desired objectives. alternatively, ranges from 1 minute to 1.5 hours. The reaction temperature of the polymerization or oligo In an embodiment, the oligomerization produces alpha merization reaction can be any reaction temperature required olefins having at least four carbon atoms. In further embodi to produce the desired polymerization or oligomerization 15 ments, the oligomerization to produce alpha olefins having product (Such as polyethylene or alpha olefins). In some at least four carbon atoms can be characterized by a single embodiments, the reaction temperature for the polymeriza pass conversion of ethylene of at least about 35 weight tion or oligomerization reaction can range from -20° C. to percent; alternatively, at least 45 percent; alternatively, at 200° C. In some embodiments, the polymerization or oli gomerization temperature ranges from 0° C. to 150° C.; least 50 percent; alternatively, at least 55 percent; alterna alternatively, ranges from 10° C. to 150° C.; alternatively, tively, at least 60 percent. ranges from 20° C. to 100° C.; or alternatively, ranges from In an aspect, the oligomerization process utilizing the C-diimine metal complex can produce alpha olefins. In some 30° C. to 80° C. embodiments, the product comprises linear alpha olefin The reaction pressure of the polymerization or oligomer having at least 4 carbon atoms. Generally, the oligomeriza ization reaction can be any reaction pressure required to 25 produce the desired polymerization or oligomerization prod tion process producing alpha olefins having at least four uct (such as polyethylene or alpha olefins). In some embodi carbon atoms produces a distribution of several alpha olefins ments, the polymerization or oligomerization reaction pres that can be described by a Schulz-Flory chain growth factor Sure can be greater than 0 psig (0 KPa); alternatively, greater K, where K is defined by the equation: than 50 psig (344 KPa); alternatively, greater than 100 psig 30 (689 KPa); or alternatively, greater than 150 psig (1.0 MPa). In other embodiments, the polymerization or oligomeriza wherein X is the number of moles of alpha olefin pro tion reaction pressure can range from 0 psig (0 KPa) to 5,000 duced having q+2 carbon atoms and X, is the number of psig (34.5 MPa); alternatively, 50 psig (344 KPa) to 4,000 moles of alpha olefin produced having in carbon atoms (i.e. psig (27.6 MPa); alternatively, 100 psig (689 KPa) to 3,000 35 the moles of the preceding alpha olefin produced). In some psig (20.9 MPa); or alternatively, 150 psig (1.0 MPa) to embodiments, the alpha olefin product distribution can be 2,000 psig (13.8 MPa). In embodiments wherein the mono described as having a Schulz-Flory chain growth factor K mer is a gas (e.g. ethylene), the polymerization or oligo less than 0.95; alternatively, less than 0.9; alternatively, less merization reaction can be carried out under a monomer gas than 0.9; or alternatively, less than 0.80. In other embodi pressure. When the polymerization or oligomerization reac 40 ments, the alpha olefin product distribution can be described tion produces polyethylene or alpha olefins, the reaction as having a Schulz-Flory chain growth factor Krange from pressure can be the monomer ethylene pressure. In some 0.4 to 0.95; alternatively, from 0.45 to 0.9; alternatively, embodiments, the ethylene pressure can be greater than 0 from 0.5 to 0.85; or alternatively, from 0.55 to 0.8. Gener psig (0 KPa); alternatively, greater than 50 psig (344 KPa): ally, the Schulz-Flory growth factor can be measured using alternatively, greater than 100 psig (689 KPa); or alterna 45 the number of moles alpha olefins of any two adjacent tively, greater than 150 psig (1.0 MPa). In other embodi produced alpha olefins. One skilled in the art will recognize ments, the ethylene pressure can range from 0 psig (0 KPa) that the measured Schulz-Flory growth factor may not be to 5,000 psig (34.5 MPa); alternatively, 50 psig (344 KPa) exactly the same using the number of moles of alpha olefin to 4,000 psig (27.6 MPa); alternatively, 100 psig (689 KPa) produced for every possible adjacent pair of produced alpha to 3,000 psig (20.9 MPa); or alternatively, 150 psig (1.0 50 olefins. Thus, in some embodiments, the Schulz-Flory MPa) to 2,000 psig (13.8 MPa). In some cases when growth factor can be an average of two or more adjacent ethylene is the monomer, inert gases can form a portion of pairs of produced alpha olefins. the total reaction pressure. In the cases where inert gases In another aspect, the oligomerization process can pro form a portion of the reaction pressure, the previously stated duce an alpha olefin product with high selectivity to linear ethylene pressures can be the applicable ethylene partial 55 alpha olefins. In some embodiments, the oligomerization pressures of the polymerization or oligomerization reaction. process produces a reactor effluent wherein the oligomerized In the situation where the monomer provides all or a portion product having 6 carbon atoms has a 1-hexene content of of the polymerization or oligomerization reaction pressure, greater than 99.0 weight%; alternatively, greater than 99.25 the reaction system pressure can decrease as the gaseous weight %; alternatively, greater than 99.5 weight %; or monomer is consumed. In this situation, additional gaseous 60 alternatively, greater than 99.75 weight%. In other embodi monomer and/or inert gas can be added to maintain a desired ments, the oligomerization process produces a reactor efflu polymerization or oligomerization reaction pressure. In ent wherein the oligomerized product having 8 carbon atoms embodiments, additional gaseous monomer can be added to a 1-octene content of greater than 98.0 weight %; alterna the polymerization or oligomerization reaction at a set rate tively, greater than 98.5 weight%; alternatively, greater than (e.g. for a continuous flow reactor), at different rates (e.g. to 65 99.0 weight%; or alternatively, greater than 99.5 weight %. maintain a set system pressure in a batch reactor). In other In yet other embodiments, the oligomerization process pro embodiments, the polymerization or oligomerization reac duces a reactor effluent wherein the oligomerized product US 7,271,121 B2 85 86 having 10 carbon atoms a 1-decene content of greater than 97.0 weight %; alternatively, greater than 97.5 weight %; TABLE 8-continued alternatively, greater than 98.0 weight %; alternatively, greater than 98.5 weight %; or alternatively, greater than Compounds of Examples 1-9 99.0 weight %. In yet other embodiments, the oligomeriza 5 tion process produces a reactor effluent wherein the oligo merized product having 6 carbon atoms comprises any weight percent 1-hexene as described herein, the oligomer ized product having 8 carbon atoms comprises any weight 10 percent 1-octene as described herein, and the oligomerized product having 10 carbon atoms comprises any weight O percent 1-decene as described herein. For example, in embodiments, the oligomerization process produces a reac tor effluent wherein the oligomerized product having 6 15 carbon atoms comprises greater than 99.0 weight percent C-Acylimine Compound III 1-hexene, the oligomerized product having 8 carbon atoms comprises greater than 99.0 weight percent 1-octene, and the oligomerized product having 10 carbon atoms comprises greater than 99 weight percent 1-decene.

EXAMPLES

The data and descriptions provided in the following 25 21 N21 examples are given to show particular embodiments of the catalysts and methods disclosed, and to demonstrate a num S N N-1 N ber of the practices and advantages thereof. The examples W V C C are given as a more detailed demonstration of some of the 30 embodiments described above, and are not intended to limit the specification or the claims to follow in any manner. Table Structure I 8 provides the Structures of the compounds and metal complexes of examples 1-9. 35 TABLE 8

Compounds of Examples 1-9

40

45

Structure II

50 C-Acylimine Compound I

55

60

w C-Acylimine Compound II 65 Structure III US 7,271,121 B2 87 88

TABLE 8-continued TABLE 8-continued

Compounds of Examples 1-9 Compounds of Examples 1-9

10 ( ) N21 C)

15 / \ - C / VCl s Structure IV Structure VIII

25 SR)

30 r

C

Structure IX 35

40

45

Structure X 50 Structure VI

55

/ \-1 N 60 o W V C Cl

Structure VII 65 Structure XI US 7,271,121 B2 89 90

TABLE 8-continued TABLE 8-continued

Compounds of Examples 1-9 Compounds of Examples 1-9

N S 1. V

Structure XVI Structure XII

25

C

Structure XVII 30

Structure XIII 35

40 Structure XVIII

45

Structure XIV

50

Structure XIX

55

60

Structure XV Structure XX 65 US 7,271,121 B2 91 92 Characterized by "H NMR (400 MHz, CDC1): 1.24, s, 9H: TABLE 8-continued 1.31, s, 9H; 6.80, s, 1H: 6.88, d. 1H: 7.23, d. 1H (resonance partially covered by CDC1, peak): 7.40, t, 1H: 7.44, d. 1H: Compounds of Examples 1-9 7.81, t, 1H: 7.97, d, 1 H; 8.17, d. 2H. Example 3

Synthesis of the C-Diimine Metal Complex Having Struc ture I A Solution containing 0.10 mL (1.0 mmol) of 2-aminom 21SR) 10 ethylpyridine in 50 mL of anhydrous butanol was added via cannula to 0.285 g (1.0 mmol) of C-acylimine compound III and 0.127 g (1.0 mmol) of anhydrous FeCl. The initially (). COC orange solution turned dark brown within 5 minutes and M. V C C deposited a dark green Solid after stirring overnight under 15 argon at 55° C. The solid was filtered, washed with 6 mL of THF, and dried to yield 0.242 g (60%) of dark green product. Structure XXI Example 4

Synthesis of the C-Diimine Metal Complex Having Struc ture II A Solution containing 0.10 mL (1.0 mmol) of 2-aminom ethylpyridine in 50 mL of anhydrous butanol was added via cannula to 0.342 g (0.91 mmol) of C-acylimine compound I and 0.127 g (1.0 mmol) of anhydrous FeCl. The initially 25 orange solution turned dark green within 20 min and depos ited a dark green Solid after stirring overnight under argon at 55° C. The solid was filtered, washed with 6 mL of THF, and dried to yield 0.449 g (80%) of dark green product. Structure XXII 30 Example 5 Example 1 Synthesis of the C-Diimine Metal Complex Having Struc Synthesis of C.-Acylimine Compound I ((2E)-2-(2,6-diiso ture III A solution of 0.297 g (1.3 mmol) of 2-(diphenylphos propylphenyl)iminoacenaphthylen-1 (2H)-one) 35 An ethanol (65 mL) solution of acenaphthenequinone phino)ethylamine in 40 mL of anhydrous butanol was added (2.00 g, 11.0 mmol) was treated with 1 mL of formic acid, via cannula to 0.440 g (1.30 mmol) of O-acylimine com followed by slow, dropwise addition (over approx. 8 hrs) of pound I and 0.164 g (1.3 mmol) of anhydrous FeCl. The a solution of 2,6-diisopropylaniline (1.56 mL, 8.22 mmol) in solution was stirred overnight under argon at 55° C. The 65 mL of ethanol. The resulting mixture was stirred at 60° solid that formed was filtered, washed with a small amount C. overnight, cooled and filtered to remove unreacted 40 of THF, and dried to give 0.505 g (58%) of dark green acenaphthenequinone. After removal of Solvent under product. Recrystallization from acetonitrile yielded X-ray vacuum, the resulting orange solid was dissolved in ether, quality crystals. The obtained crystals were Subjected to filtered and cooled to -10° C. overnight. The orange solid X-ray crystallography. An ORTEP diagram for the crystals that deposited was filtered, washed with cold ether and produced in this example is shown in FIG. 1. Selected bond dried. The filtrate was again cooled to -10°C. overnight and 45 distance and bond angle for catalyst BMS-114 include: additional orange solid was isolated, giving a total yield of Fe C11–2.286; Fe C12 2.313; Fe N1–2.181; 1.91 g (68.5%). Characterized by H NMR (400 MHz, Fe N2 2.166; Fe P1- 2.497; P1-Fe N2 -135.19; CDC1): 0.88 d. 6H; 1.15, d. 6H; 2.82, m, 2H; 8.18, t, 1H: P1-Fe C11-100.77; N2-Fe C11- 93.70: N1-Fe C11 7.99, d. 1H: 7.81, t, 1H: 7.39, t, 1H: 6.62, d. 1 H. (3H's are 156.18; C11-Fe C12-111.98. obscured by the CDC1, peak). "H NMR (400 MHz, MeCN 50 Example 6 d): 0.89 d. 6H; 1.10, d. 6H; 2.79, m, 2H; 8.27, d. 1H; 8.12. m, 2H; 7.87, t, 1H: 7.45, t, 1H 7.30, m, 3H; 6.60, d.1 H. Example 2 Synthesis of the C-Diimine Metal Complex Having Struc ture IV A solution of 0.211 g (0.92 mmol) of 2-(diphenylphos Synthesis of C-Acylimine Compound II ((2E)-2-(2,5-di-t- 55 phino)ethylamine in 40 mL of anhydrous butanol was added butylphenyl)iminoacenaphthylen-1 (2H)-one) via cannula to 0.263 g (0.92 mmol) of O-acylimine com An ethanol (65 mL) solution of acenaphthenequinone pound III and 0.117 g (0.92 mmol) of anhydrous Fe(Cl. The (2.00 g, 11.0 mmol) was treated with 1 mL of formic acid, solution was stirred overnight under argon at 55° C. The followed by slow, dropwise addition (over approx. 8 hrs) of solid that formed was filtered, washed with a small amount a solution of 2,5-di-t-butylaniline (1.69 g, 8.25 mmol) in 65 60 of THF, and dried to give 0.380 g (66%) of dark green mL of ethanol. The resulting mixture was stirred at 60° C. product. overnight, cooled and filtered to remove unreacted acenaph Example 7 thenequinone. After removal of solvent under vacuum, the resulting orange Solid was dissolved in ether, filtered and cooled to -10°C. overnight. The orange solid that deposited Synthesis of the C-Diimine Metal Complex Having Struc was filtered, washed with cold ether and dried. The filtrate 65 ture V was again cooled to -10° C. overnight and more orange A 0.202 g sample of 2-aminoethyl(4-chlorophenyl) sul solid was isolated, giving a total yield of 2.13 g (70%). fide (0.93 mmol. 80% pure) was purged with argon for 20 US 7,271,121 B2 93 94 min and then added by cannula to 40 mL of anhydrous solution was stirred overnight under argon at 55° C. The butanol. This solution was transferred by cannula to 0.265 g resulting dark green Solution was reduced in Volume to 5 mL. (0.93 mmol) of O-acylimine compound III and 0.118 g (0.93 in vacuo, depositing a green solid. This solid was filtered, mmol) of anhydrous FeCl2. The resulting solution was stirred for two days under argon at 55°C. The dark solid that washed with diethyl ether and dried to give 0.352 g (49%) formed was filtered, washed with a small amount of THF, 5 of green product. Recrystallization was done in MeCN. and dried to give 0.203 g (39%) of green product. Recrys tallization from acetonitrile gave long, rod-like crystals. The Example 9 obtained crystals were subjected to X-ray crystallography. An ORTEP diagram for the crystal produced in this example Polymerization procedure: In separate runs, each of the shown in FIG. 2. Selected bond distance and bond angle 10 complexes listed in Table 9 (prepared as a standard solution or the crystals include: Fe(1)-N(1)=2.132 A: Fe(1)-N(2)=2.197 A. The X-ray crystal structure for the in methylene chloride, O aS a homogeneous mixture in material and the ethylene oligomerization example provided biphenyl) was placed in an NMR tube in a substantially in Table 9 indicate that it is not required that the metal oxygen- and moisture-free environment. If the biphenyl complexing group of the C-diimine metal complex for a mixture was used, about 0.5 ml of methylene chloride was dative (complexing) bond with the metal atom to have an added to the tube. The NMR tube was then sealed and active ethylene oligomerization catalyst when the C-diimine affixed (using copper wire) to the internal stirring mecha metal complex is contacted with ethylene and a cocatalyst. nism of a 500 ml stainless steel autoclave, such that the Additionally, the X-ray crystal structure indicates that the beginning of stirring would break the NMR tube and release g-diimine metal complexes may be isolated in a dimeric the contents into the reactor. The reactor was then evacuated formethylene (having oligomerization bridging halogen catalyst atoms) when theand C-diimine have an activemetal 20 andd charged withwin anhydrannyarous solventlvent thatunal containedtained thune complex is contacted with ethylene and a cocatalyst. aluminum cocatalyst. The reactor was then pressurized with ethylene, and stirring was commenced to initiate the reac Example 8 tion. Ethylene pressure was held constant and reaction temperature was controlled at the temperature set point by 25 internal cooling coils. Each reaction was commenced at Synthesis of the C-Diimine Metal Complex Having Struc- about 30° C.; for selected reactions a maximum exotherm is ture VI shown in Table 9. At the end of each reaction, the ethylene A solution of 0.235 g (1.02 mmol) of 2-(diphenylphos- was slowly vented, and the products were analyzed by gas phino)ethylamine in 40 mL of anhydrous butanol was added chromatography using the solvent as the internal standard. via cannula to 0.377 g (1.02 mmol) of O-acylimine com- The Schulz-Flory constant K was used to estimate the total pound II and 0.130 g (1.02 mmol) of anhydrous Fe(Cl. The amount of product made.

TABLE 9 Ethylene Polymerization Results Catalyst Produc Struc- Amt Pethylene Solvent Length T Ta Yield tivity K value C6% Cs 96 Co. 96 Entry ture (mg) Cocatalyst. Al:Fe (psig) (ml) (min) (C.) (C.) (g) (Ibib cat) (C2, Co) purity purity purity 1 II 6.O MMAO 500 400 Heptane, 100 60 55 56 50 8,300 --O.S 99.1 98.8 98.6 2 VII 4.O MMAO 500 400 Heptane, 100 30 30 NA 3 VIII 4.O MMAO 500 400 Heptane, 100 30 30 NA 4 II 4.O MMAO 500 400 Heptane, 100 10 55 57 43 11,000 0.61 99.1S 98.92 98.75 5 II 4.O MMAO 500 400 Heptane, 100 30 55 62 69 17,000 O.6O 99.17 98.92 98.85 6 II 1.O MMAO 1000 400 Heptane, 100 30 40 42 31 31,000 O.6O 99.6O 99.26 99.25 7 IX 4.O MMAO 500 400 Heptane, 100 10 30 NA 8 X 4.O MMAO 500 400 Heptane, 100 30 30 NA 9 X 4.O MMAO 500 400 Heptane, 100 30 30 &S 10 XII 4.O MMAO 500 400 Heptane, 100 30 30 NA 11 6.O MMAO 500 400 Heptane, 100 30 30 &S 12 IV 4.O MMAO 500 400 Heptane, 100 30 55 61 90 22,000 O.42 99.16 98.62 97.97 13 V 4.O MMAO 500 400 Heptane, 100 30 50 52 31 7,700 O.64 98.95 97.43 14 V 4.O MMAO 500 650 Heptane, 200 30 45 45 15 7300 PE 15 II 2.0 MMAO 500 400 Heptane, 200 30 55 57 153 76,000 -0.6 16 II 1.O MMAO 1000 400 Heptane, 200 60 50 S4 83 83,000 O.6O 99.86 99.88 99.36 17 XIII 4.O MMAO 500 400 Heptane, 200 60 40 46 21 5,400 0.61 98.62 98.7O 97.54 18 II O.8 MMAO 1000 800 Heptane, 200 30 50 71 94 117,000 O.S9 99.7O 99.63 99.04 2O II 1.O MMAO 1000 400 Heptane, 200 60 50 71 85 85,000 0.61 99.82 99.81 99.39 21 II O.4 MMAO 2000 800 Heptane, 200 60 40 43 16 40,000 O.S4 99.52 99.06 22 XIV 4.O MMAO 500 650 Heptane, 200 60 40 42 30 7,400 O.49 99.2O 98.54 97.67 23 XV 4.O MMAO 500 650 Heptane, 200 30 35 37 6.4 1,600 O.60 ind ind ind 24 XVI 4.O MMAO 500 400 Heptane, 100 2O 30 NA 25 IV 2.0 MMAO 1000 400 Heptane, 100 30 50 51 45 22,500 0.45 97.93 97.57 97.68 26 XVII 4.O MMAO 500 400 Heptane, 100 15 30 NA 27 XVIII 4.O MMAO 500 400 Heptane, 100 25 30 NA 28 XIX 4.O MMAO 500 400 Heptane, 100 30 30 NA 29 XX 4.O MMAO 500 400 Heptane, 100 2O 30 NA 30 XXI 4.O MMAO 500 650 Heptane, 200 30 35 35 4.8 1200 -0.6 87.3 31 XXII 8.O MMAO 500 650 Heptane, 400 60 35 37 NA US 7,271,121 B2 95 96 While preferred embodiments of the invention have been tional groups, or a hydrocarbyl group; R' to/through R' shown and described, modifications thereof can be made by can each independently be hydrogen O hydrocarbyl group; one skilled in the art without departing from the spirit and and m can be 2 or 3. teachings of the invention. The embodiments described herein are exemplary only, and are not intended to be 5 2. The method of claim 1 wherein the method comprises: limiting. Many variations and modifications of the invention a) contacting an O-acylimine compound having a Struc disclosed herein are possible and are within the scope of the ture 37b: invention. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of Sructure 37b like magnitude falling within the expressly stated ranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4, Ra2 Rall etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). Use of the term “optionally' with respect to any element of a claim Ra13 N is intended to mean that the Subject element is required, or alternatively, is not required. Both alternatives are intended 15 to be within the scope of the claim. Use of broader terms Ra14 Ra15 Such as comprises, includes, having, etc. should be under- R51 stood to provide Support for narrower terms such as con sisting of consisting essentially of comprised substantially of etc. 2O Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow, that scope including all equivalents of the FeCl, and a primary amine having a Structure: Subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the 2s present invention. Thus, the claims are a further description Rc73 Rc75 and are an addition to the preferred embodiments of the present invention. The discussion of a reference in the Description of Related Art is not an admission that it is prior Rc71 Rc77 art to the present invention, especially any reference that may have a publication date after the priority date of this 30 Re79 application. The disclosures of all patents, patent applica- NH-(CH)-P Rc80 tions, and publications cited herein are hereby incorporated by reference, to the extent that they provide exemplary, procedural or other details supplementary to those set forth Rc72 R78; and herein. 35 Rc74 Rc76 What is claimed is: 1. A method for producing an O-diimine metal complex comprising forming at least one imine bond in the presence 40 b) recovering the C-diimine metal complex. of a metal salt, metal complex, or combinations thereof, 3. The method of claim 2, wherein the O-acylimine wherein the C-diimine metal complex has the formula: compound is derived from acenaphthenequinonc and the 78 C-acylimine nitrogen group of the O-acylimine compound

C Rc77 R cF6 consists of a 2,6-disubstituted phenyl group. Rc75 R as 4. The method of claim 3, wherein the primary amine is Re78 Re89 2-(diphenylphosphino)ethylamine or 3-(diphenylphos Rc73 Re74 phino)propylamine. 5. The method of claim 4 wherein the C-diimine metal Rc71 Rc72 complex has a formula: 50 Ral Rall P(CH2)m 'd 60 /V wherein R' to/through R' can each independently be hydrogen, an organyl group consisting of inert functional groups, a hydrocarbyl group, or inert functional groups; R 65 to/through R can each independently be hydrogen, an 6. The method of claim 4 wherein the C-diimine metal organyl group, an organyl group consisting of inert func- complex has a formula: US 7,271,121 B2 98 10. The method of claim 2 wherein the C-diimine metal complex has a formula:

10

7. The method of claim 4 wherein the C-diimine metal 15 complex has a formula:

11. The method of claim 2 wherein the O-acylimine compound is prepared by: a) contacting an O-acyl compound having a Structure 10:

25 Structure 10 O O

30 R C R52

8. The method of claim 4 wherein the C-diimine metal R53 R54 complex has a formula: R55 R56 35 and a primary amine having a Structure 3a:

40 Structure 3a Ra12 Rall

Ra13 NH2; and 45 Ra14 Ra15

b) recovering the O-acylimine compound. 9. The method of claim 4 wherein the C-diimine metal 50 12. The method of claim 1, wherein the method com complex has a formula: prises: a) contacting an O-acylimine metal complex having a Structure:

55

Ra2

60 Ra13

Ral4 \ C Cl 65 US 7,271,121 B2 99 100 and a primary amine having a Structure: and a primary amine having a Structure 3a:

Rc3 Rc75 Structure 3a Ra2 Rall

Rc71 Rc77 Ra13 NH2:

NH-(CH)-P 10 Ra14 Ra15 b) recovering the O-acylimine compound; Rc72 Re?8. and c) contacting the O-acylimine compound with FeCl; and d) recovering the C-acylimine metal complex. 15 16. The method of claim 12 wherein the O-acylimine Re74 Rc76 metal complex is prepared by: a) contacting an contacting an O-acyl compound having a b) recovering the C-dimine metal complex. Structure 10: 13. The method of claim 12, wherein the O-acylimine compound in the C-acylimine metal complex is derived from Structure 10 acenaphthenequinone, the C-acylimine nitrogen group of the O O C-acylimine compound of the O-acylimine metal complex consists of a 2,6-disubstituted phenyl group. 14. The method of claim 13, wherein the primary amine 25 R C) R52, is 2-(diphenylphosphino)ethyiamine or 3-(diphenylphos phino)propylamine. 15. The method of claim 12, wherein the O-acylimine R53 R54 metal complex is prepared by: 30 R55 R56 a) contacting an contacting an O-acyl compound having a Structure 10: FeCl and a primary amine having a Structure 3a:

Structure 10 35 O O Structure 3a Ra2 Rall

R C) R52 Ra13 NH2; and 40 R53 R54 Ra14 Ra15 R55 R56 b) recovering the O-acylimine metal complex.

k k k k k UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 7,271,121 B2 Page 1 of 1 APPLICATIONNO. : 11/186039 DATED : September 18, 2007 INVENTOR(S) : Brooke L. Small et al. It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

Column 95, claim 1, lines 42-62 replace

t of8 17 R Rs76. Re6 Riis Rise R79 Rig R4 R73 R

R2 K'i 72 R. I (CH: -(c)) '). -- CF ch; RS rr s Ri N But R. y ("YC-y- Rii Ris R. I. RS R.- 3. Rs. 86

66 Rs: Rs: 99 With 3. R

Column 96, claim 2, line 9, replace "Sructure 37b with -- Structure 37b --

Signed and Sealed this Second Day of October, 2012

David J. Kappos Director of the United States Patent and Trademark Office UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 7,271,121 B2 Page 1 of 1 APPLICATIONNO. : 11/186039 DATED : September 18, 2007 INVENTOR(S) : Brooke L. Small et al. It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

In the Specifications Column 8, line 35, replace "3,4-dibydronaphthoguinone with --3,4-dihydronaphthoguinone-- Column 16, line 26, replace “2,6-dilsopropylaniline with --2,6-diisopropylaniline Column 16, line37, replace “R' with --R"-- Column 17, lines 9 & 10, replace “2,6-dimethyiphenyl group, a 2,6-diethyiphenyl group with --2,6-dimethylphenyl group, a 2,6-diethylphenyl group-- Column 17, line 13, replace “2,6-dimethyiphenyl with --2,6-dimethylphenyl Column 17, line 16, replace “2,6-dimethyiphenyl with --2,6-dimethylphenyl Column 17, lines 16 & 17, replace “2,6-diethyiphenyl with --2,6-diethylphenyl Column 17, line 18, replace “2,6-di-tert-butyiphenyl with --2,6-di-tert-butylphenyl Column 17, line 19, replace “2,5-di-tert-butyiphenyl with --2,5-di-tert-butylphenyl Column 25, line 8, replace “R” to/through R” with --R" to/through R'-- Column 34, line 56, replace “Table 2) with --(Table 2)-- Column 36, line 13, replace “iron(II) with -iron(III)-- Column 36, line 34, delete duplicate “metal salt Column 66, line 25, replace “14, with --1-4- Column 66, line 34, replace “14, with --1-4- Column 73, line 13, replace “1:1 with -1.1:1-- Column 78, line 42, replace “2,6-disubsituted with --2,6-disubstituted Column 80, line 52, replace “odiimine with --"o-diimine-- Column 81, line 7, replace “2,6-dilsopropylphenyl with --2,6-diisopropylphenyl Column 81, line 18, replace “2,6-dilsopropylphenyl with --2,6-diisopropylphenyl Column 82, line 24, delete “alternatively In the Claims Column 99, line 26, replace “2-(diphenylphosphino)ethyiamine with --2-(diphenylphosphino)ethylamine-- Column 99, line 31, delete duplicate “contacting an Column 100, line 17, delete duplicate “contacting an

Signed and Sealed this Twenty-eighth Day of May, 2013

Teresa Stanek Rea Acting Director of the United States Patent and Trademark Office UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 7,271,121 B2 Page 1 of 1 APPLICATIONNO. : 11/186039 DATED : September 18, 2007 INVENTOR(S) : Brooke L. Small et al. It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

In the Claims:

Column 96, line 42, replace “acenaphthenequinonc with -acenaphthenequinone--

Signed and Sealed this Ninth Day of July, 2013 2 2-Y xx 26-e-s? 2.*é-...sé -13 . . Teresa Stanek Rea Acting Director of the United States Patent and Trademark Office