(12) United States Patent (10) Patent No.: US 6,169,208 B1 Lee (45) Date of Patent: Jan

USOO6169208B1 (12) United States Patent (10) Patent No.: US 6,169,208 B1 Lee (45) Date of Patent: Jan. 2, 2001

(54) PROCESS FOR PRODUCING A MAGNESIUM Goldberg et al., “Synthesis of Sodium Tetrakis(3,5-DI(Tri DITETRAKIS(ARYL)BORATE AND fluoromethyl)Phenyl Borate”, Zhurnal organicheskoi PRODUCTS THEREFROM Khimi, 1989, vol. 25, No. 5, pp. 1099–1102 (translation thereof), pp. 989-991. (75) Inventor: John Y. Lee, Baton Rouge, LA (US) Golden et al., “Lithium-Mediated Organofluorine Hydrogen Bonding: Structure of Lithium Tetreakis(3,5-bis(trifluorom (73) Assignee: Albemarle Corporation, Richmond, ethyl)phenyl)borate Tetrahydrate”, Inorg. Chem. vol. 33, VA (US) 1994, pp. 5374–5375. Hayashi et al., “A Novel Chiral Super-Lewis Acidic Cata (*) Notice: Under 35 U.S.C. 154(b), the term of this lyst for Enantioselective Synthesis”, J. Am. Chem. Soc., patent shall be extended for 0 days. 1996, vol. 118, No. 23, pp. 5502–5503. Hughes et al., “Synthesis and Structure of the Thallium(I) (21) Appl. No.: 09/453,606 Salt of the Tetrakis {3,5-bis(trifluoromethyl)phenylborate Anion”, Inorg. Chem. vol. 36, 1997, pp. 1726–1727. (22) Filed: Dec. 3, 1999 Jia et al., “Cationic Metallocene Polymerization Catalysts (51) Int. Cl." ...... C07F 5/02 Based on Tetrakis(pentafluorophenyl)borate and Its Deriva (52) U.S. Cl...... 568/6; 568/1 tives. Probing the Limits of Anion “Noncoordination” via a (58) Field of Search ...... 568/1, 6 Synthetic, Solution Dynamic, Structural, and Catalytic Ole fin Polymerization Study', Organometallics, 1997, vol. 16, (56) References Cited p. 842-857. Jia et al., “Protected (Fluoroaryl)borates as Effective Coun U.S. PATENT DOCUMENTS teranions for Cationic Metallocene Polymerization Cata 4,808.282 2/1989 Gregory ...... 204/58.5 lysts”, Organometallics, vol. 14, 1995 pp. 3135-3137. 5,070,161 12/1991 Nakano et al. ... 526/193 Chem. Abstract #17030, Line H, Myl, et al., “Preparation of 5,078.974 1/1992 Ashby et al...... 422/187 Sodium Tetraphenylborate”, Benzene Derivatives, 10-E 5,096,936 3/1992 Seko et al...... 522/31 Benzene derivatives, 1959, 1 page. 5,189,222 2/1993 Ashby et al...... 568/1 5,223,591 6/1993 Nyander et al...... 526/204 Nesmeyanov et al., “Synthesis of Sodium Tetraphenylbo 5,340,898 8/1994 Cavezzan et al...... 528/19 ron”, IZV. Akad. Nauk SSSR, Otd. Khim. Nauk, 1955, pp. 5,399,781 3/1995 Doellein ...... 568/6 187. (Translation pp. 167). 5,468,902 11/1995 Castellanos et al...... 568/6 Nishida et al., “Tetrakis(3,5-bis(trifluoromethyl)phenylbo 5,473,036 12/1995 Piotrowski et al...... 528/4 rate. Highly Lipophilic Stable Anionic Agent for Solven 5,488,169 1/1996 Ikeda et al...... 568/3 t-extraction of Cations”, Bull Chem. Soc. Jpn., vol. 57, No. 5,493,056 2/1996 Ikeda et al...... 568/6 9, 1984, pp. 2600–2604. 5,510,536 4/1996 Ikeda et al...... 568/6 5,514,728 5/1996 Lamanna et al...... 522/31 (List continued on next page.) 5,600,003 2/1997 Baur et al...... 568/1 5,670,682 9/1997 Sangokoya ..... 556/181 Primary Examiner Jean F Vollano 5,693,867 12/1997 Bauer et al...... 568/1 (74) Attorney, Agent, or Firm-Philip M. Pippenger 5,919,983 7/1999 Rosen et al...... 568/3 (57) ABSTRACT FOREIGN PATENT DOCUMENTS A Solution comprising a halomagnesium tetrakis(aryl) 0331496 9/1989 (EP). O913400 5/1999 (EP). borate in a liquid organic medium, wherein the liquid 2727416 5/1996 (FR). organic medium is comprised of one or more liquid dihy 92.95984 11/1997 (JP). drocarbyl ethers, one or more liquid hydrocarbons, one or 92.95985 11/1997 (JP). more liquid halogenated hydrocarbons, or mixtures thereof, 1O-316686 12/1998 (JP). is contacted with water. This produces magnesium 98.07798 2/1998 (WO). ditetrakis(aryl)borate) in the organic phase of a two-phase 9822470 5/1998 (WO). water/liquid organic medium. The magnesium ditetrakis (aryl)borate) can be, but need not be, isolated. A protic OTHER PUBLICATIONS ammonium Salt, an onium Salt, or a triarylmethyl Salt can be Bahr et al., “Trityl Tetrakis(3,5-bis(trifluoromethyl)phe reacted with the magnesium ditetrakis(aryl)borate) to pro nyl)-borate: A New Hybride Abstraction Reagent”, J. Org. duce the corresponding protic ammonium, onium, or triaryl Chem., 1992, vol. 57, No. 20, pp. 5545–5547. methyl tetrakis(aryl)borate. The magnesium ditetrakis Brookhart et al., “I(3,5-(CF)2CH i) BHH(OEt): A (aryl)borate) can instead be reacted with a metal salt to Convenient Reagent for Generation and Stabilization of form a metal tetrakis(aryl)borate. The produced metal Cationic, Highly Electrophilic Organometallic Complexes', tetrakis( aryl)borate can be further reacted with a protic Organometallics, vol. 11, 1992, pp. 3920-3922. ammonium Salt, an onium Salt, or a triarylmethyl Salt to yield Chien et al., “Isospecific Polymerization of Propylene Cata a protic ammonium, onium, or triarylmethyl tetrakis(aryl) lyzed by rac-Ethylenebis(indenyl)methylzirconium”, Cat borate. Certain of these tetrakis(aryl)borates can be con ion Journal Am. Chem. Soc. 1991, vol. 113, pp. 8570–8571. Veniently purified via the formation of a liquid clathrate at Fujiki et al., “Synthesis and Lipophilicities of Tetraarylbo ambient temperatures. rate ions substituted with many Trifluoromethyl Groups', Journal of Fluorine Chemistry, vol. 57, 1992, pp. 307-321. 62 Claims, No Drawings US 6,169,208 B1 Page 2

OTHER PUBLICATIONS Chemical Abstract, # 129:317638z, of WO 9846,647, 1998, Vandeberg et al., “Studies in the Tetraarylborates Part III. p. 831. The Preparation and Reagent Properties of Sodium Tetrak Atwood, Jerry L., Coordination Chemistry of Aluminum, is(p-Trifluoromethylphenyl) Borate and Sodium Tetrak Chapter 6, “Anionic and Cationic Organoaluminum Com is(m-Fluorophenyl) Borate', Analytica Chimica Acta, pounds”, 1993, p. 197-232. Elsevier Publishing Company, Amsterdam, 1969, vol. 44, Chemical Abstract, #214696R, Wakabayshi et al., “Pyri pp. 175-183. dinium and Quinolinium Tetraphenylborate Salts as Agro Chemical Abstract, #15921, line G., Vit, Jaroslav, “Preparing chemical and Industrial Microbicides”, Organometallics, Sodium Tetraaylborates, esp. Sodium Tetraphenylborate”, 1989, vol. 111, p. 611. Organometallic Compounds, vol. 64, 1966, col. 15921, 1 page. Wittig et al., “Uber Komplexbildung mit Triphenyl-bor (III. Chemical Abstract, # 124402W, Wakabayashi et al., “Agro Mitt)", Annalen der Chemie, 1951, vol. 573, pp. 195-209. chemical and Industrial Microbicides Containing Tetraphe Coleman et al., “Air-Stable Liquid Clathrates. 1. Crystal nylborates”, 1988, vol. 109, p. 254. Structure of NBuBrand Reactivity of the NBuBr-5 Chemical Abstract, #6607, Line D, Wittig et al., “Complex C.H. Liquid Clathrate”, Journal of Crystallographic and Formation with Triphenylboron. III.'', 1951, vol. 46, 1 page. Spectroscopic Research, vol. 20, No. 2, 1990, pp. 199-201. Chemical Abstract, #85:86471u, Kholkin et al., “Synthesis of Metal Tetraphenylborates by the Exchange Extraction Chem. Abstract, vol. 110, 1989, of JP 63,108,074, 1988, p. Method”, IZV. Sib. Otd. Akad. Nauk., 1976, p. 565. 720, #125211 P. Chemical Abstract, #125: 196680p, of FR 2,727,416, 1996, “Periodic Table of the Elements”, Chem. And Eng. News, p. 20. 1985, pp. 26–27. US 6,169,208 B1 1 2 PROCESS FOR PRODUCING AMAGNESUM organic medium is produced. Each aryl group of the tetrakis DITETRAKIS(ARYL)BORATE AND (aryl)borate has bonded directly to an aromatic ring at least PRODUCTS THEREFROM two fluorine atoms, or at least two perfluorohydrocarbyl groups, or at least one fluorine atom and at least one TECHNICAL FIELD perfluorohydrocarbyl group. The liquid organic medium is comprised of one or more liquid dihydrocarbyl ethers, one This invention relates to a method for making a magne sium ditetrakis(aryl)borate), which can be further reacted or more liquid hydrocarbons, one or more liquid haloge with an organic cation Salt to produce the corresponding nated hydrocarbons, or mixtures thereof. organic cation tetrakis(aryl)borate. When the organic cat The borate anion has four fluorine-containing aryl groups, ion is a protic ammonium cation or a triarylmethyl cation, each of which has bonded directly to an aromatic ring at the tetrakis(aryl)borate salt is useful as a cocatalyst for least two fluorine atoms, or at least two perfluorohydrocar metallocene-catalyzed polymerization. When the organic byl groups, or at least one fluorine atom and at least one cation is an onium cation, the tetrakis(aryl)borate salt is perfluorohydrocarbyl group. It is preferred that at least two useful as an initiator in the crosslinking of polyorganosilox fluorine atoms, or at least two perfluorohydrocarbyl groups 15 are bonded directly to an aromatic ring. Each position on the CS. aromatic ring(s) of the aryl group that is not a fluorine atom BACKGROUND or a perfluorohydrocarbyl group is Substituted by a hydrogen atom, a hydrocarbyl group, an alkoxy group, or a silyl group. It is known that when a halomagnesium Salt of a tetrakis The aryl groups may be the same or different from each (aryl)borate anion is obtained, other magnesium Salts are other; it is preferred that all four aryl groups are the same. usually also present. Often, the removal of these other Another embodiment of this invention is a process which magnesium Salts is necessary because they interfere with the comprises mixing at least a portion of the magnesium intended use of the halomagnesium Salt of the tetrakis(aryl) ditetrakis(aryl)borate produced in the first embodiment in borate anion. Reaction of the halomagnesium tetrakis(aryl) a liquid medium with a Salt Selected from a) a protic borate with an alkali metal Salt to form an alkali metal 25 ammonium salt, b) an onium salt, and c) a triarylmethyl salt, tetrakis(aryl)borate is a separation method that has been wherein the triarylmethyl cation has three aryl groups bound used. For various descriptions of this method, see Nishida et to a central carbon atom, to produce a protic ammonium al., Bull. Chem. Soc. Jpn., 1984, 57, 2600; Goldberg et al., tetrakis(aryl)borate, an onium tetrakis(aryl)borate, or a Zhurnal Organicheskoi Khimi, 1989, 25, 1099; Fujiki et al., triarylmethyl tetrakis(aryl)borate. The protic ammonium J. Fluorine Chemistry, 1992, 57, 307; and EP 913,400. A cation has the formula RNHCD, in which each R is method which cleanly Separates other magnesium Salts from independently a hydrocarbyl group containing up to about the halomagnesium salt of the tetrakis(aryl)borate without thirty carbon atoms, and the onium cation has the formula the introduction of a reagent Such an alkali metal salt would ERCD, wherein E is an element of any of Groups 15-17 of be desirable. the Periodic Table, wherein each R is independently a Once a Suitably pure tetrakis(aryl)borate Salt is obtained, 35 hydrocarbyl group containing up to about thirty carbon it can be reacted with an appropriate compound to yield an atoms, and wherein n is equal to the Valence of E plus one. organic cation salt of the tetrakis(aryl)borate. It is often For labeling of the groups of the Periodic Table, see for desirable to purify these organic cation tetrakis(aryl)borates. example, the Periodic Table appearing in Chemical C& Engi It is known that phenyl(dimethyl)ammonium tetrakis neering News, 1985, 69, 26. (pentafluorophenyl)borate can be purified via the formation 40 Still another embodiment of this invention is a process of a liquid clathrate. The liquid clathrate is formed in toluene which comprises mixing, in a liquid medium, at least a at temperatures typically above 55 C.; at temperatures less portion of the magnesium ditetrakis(aryl)borate) produced than about 55 C., the compound precipitates. While the in the first embodiment and at least one metal Salt. An liquid clathrate provides relatively pure phenyl(dimethyl) inorganic metal tetrakis(aryl)borate is produced. ammonium-tetrakis(pentafluorophenyl)borate, it is inconve 45 nient to keep the clathrate-containing Solution and apparatus Yet another embodiment of this invention is a process at elevated temperatures while performing necessary which comprises mixing, in a liquid medium, at least a manipulations. A more convenient purification method is portion of the metal tetrakis(aryl)borate produced in the desirable. preceding embodiment with a salt Selected from a) a protic 50 ammonium salt, b) an onium salt, and c) a triarylmethyl salt, to produce a protic ammonium tetrakis(aryl)borate, an SUMMARY OF THE INVENTION onium tetrakis(aryl)borate, or a triarylnoethyl tetrakis This invention provides for the formation of a magnesium (aryl)borate. The protic ammonium cations, onium cations, ditetrakis(aryl)borate), which can be, but need not be, and triarylmethyl cations are as described above. isolated. The magnesium ditetrakis(aryl)borate) can be 55 Further embodiments of this invention will be apparent reacted, in isolated or unisolated form, with a Salt of a from the ensuing description and appended claims. desired cation to form the desired cation tetrakis(aryl) borate. Certain of these tetrakis(aryl)borates can be con FURTHER DETAILED DESCRIPTION OF THE Veniently purified via the formation of a liquid clathrate at INVENTION ambient temperatures. 60 The liquid organic medium of the Solution that also A first embodiment of this invention is a process which comprises a halomagnesium tetrakis(aryl)borate is com comprises contacting i) a Solution comprising a liquid prised of one or more liquid dihydrocarbyl ethers, one or organic medium, which is Substantially immiscible with more liquid hydrocarbons, one or more halogenated water, and a halomagnesium tetrakis(aryl)borate, and ii) hydrocarbons, or mixtures thereof. Those ethers, water, in Such proportions that a two-phase mixture is 65 hydrocarbons, and halogenated hydrocarbons that are Sub obtained. A Solution of a magnesium ditetrakis(aryl) Stantially immiscible with water, Such that a two-phase borate in the organic phase of a two-phase water/liquid mixture will be formed, are preferred. Ethers that may be US 6,169,208 B1 3 4 used include, for example, diethyl ether, di-n-propyl ether, tetrafluoroindenyl. It is preferred that at most two diisopropyl ether, tert-butyl ethyl ether, diheptyl ether, and Substituents on the ring of the aryl group are hydrocarbyl, similar compounds. Preferred ethers are diethyl ether and perfluorohydrocarbyl, or alkoxy, while the rest of the Sub diisopropyl ether, especially diethyl ether. Suitable hydro Stituents are fluorine atoms. carbons include pentane, hexane, methylcyclohexane, It is highly preferred to have aryl groups in which the all heptane, octane, cyclooctane, nonane, benzene, toluene, and of the Substituents are fluorine atoms. Examples of Such Xylenes. Halogenated hydrocarbons that may be used groups are pentafluorophenyl, 4-nonafluorobiphenylyl, include dichlorome thane, trichloromethane, 1,2- 2-nonafluorobiphenylyl, 1-heptafluoronaphthy 1,2- dichloroethane, 1-bromo-2-chloroethane, 1-bromopropane, he pta flu or on aphthy 1, 7-n on a fluoro anthryl, (chloromethyl)cyclopropane, 1-bromobutane, 1-bromo-2- 9-nonafluorophenanthryl, and analogous groups. The most ethylbutane, 1,1-dichloro-3,3-dimethylbutane, cyclobutyl highly preferred perfluoroaryl group is pentafluorophenyl, chloride, neopentyl chloride, 1-bromo-5-chloropentane, thus, the most highly preferred borate is tetrakis cyclopentyl bromide, 1,6-dibromohexane, trans-1,2- (pentafluorophenyl)borate. dichlorocyclohexane, 1-chloroheptane, and 1,8- A magnesium ditetrakis(aryl)borate) is produced by dichlorooctane. 15 contacting water and the Solution comprising a liquid The proportions of water and liquid organic medium are organic medium and a halomagnesium tetrakis(aryl)borate. Such that either component can be present in a larger amount These components are usually at room temperature when than the other; however, a large excess of either is unnec mixed together. In the resultant two-phase mixture, the essary. Preferred ratioS of water to liquid organic medium magnesium ditetrakis(aryl)borate) is in the organic phase, are in the range of from about 0.2 parts to about three parts which can easily be separated from the aqueous phase. by Volume of water per part by Volume of liquid organic Removal of the liquid organic medium from the Separated medium. organic phase yields Solid magnesium ditetrakis(aryl) The halogen atom of the halomagnesium moiety of the borate. Magnesium salts produced in the formation of the halomagnesium tetrakis(aryl)borate may be a chlorine magnesium ditetrakis(aryl)borate) migrate to the aqueous atom, bromine atom, or iodine atom. Preferred halogen 25 layer. When other magnesium Salts are present in the liquid atoms are chlorine and bromine; most preferred is a bromine organic medium, they are also expected to be in the water atom. Thus, the most preferred halomagnesium moiety is a layer of the resultant two-phase mixture. bromomagnesium moiety. During the course of the reaction, Some heat may be Throughout this document, the term “aryl group” shall produced, raising the temperature of the reaction mixture. be understood to mean, as described above, a fluorine The mixture may be heated, provided that the temperature containing aryl group, which has bonded directly to an does not exceed the thermal decomposition temperature of aromatic ring at least two fluorine atoms, or at least two the magnesium ditetrakis(aryl)borate). A preferred contact perfluorohydrocarbyl groups, or at least one fluorine atom time for the components of the reaction is in the range of and at least one perfluorohydrocarbyl group. It is preferred from about ten minutes to about eight hours. More that at least two fluorine atoms or at least two perfluorohy 35 preferably, the contact time is from about fifteen minutes to drocarbyl groups are bonded directly to an aromatic ring. about Six hours. Each position on the aromatic ring(s) of the aryl group that For the contacting of a magnesium ditetrakis(aryl) is not a fluorine atom or a perfluorohydrocarbyl group is borate and a triarylmethyl salt, the liquid medium is com Substituted by a hydrogen atom, a hydrocarbyl group, an prised of one or more liquid hydrocarbons, halogenated alkoxy group, or a silyl group. The aromatic ring of the aryl 40 hydrocarbons, ethers, or mixtures thereof. Suitable hydro group may be, but is not limited to, benzene, naphthalene, carbons include linear, branched, and cyclic Saturated anthracene, biphenyl, phenanthrene, or indene. Benzene is hydrocarbons, and aromatic hydrocarbons. Examples of the preferred aromatic moiety. The perfluorohydrocarbyl Suitable hydrocarbons include pentane, he Xane, groups include alkyl and aryl perfluorocarbons, Suitable cyclohexane, methylcyclohexane, heptane, cyclooctane, perfluorohydrocarbyl groups are, for example, 45 nonane, benzene, toluene, Xylene, and the like. Halogenated trifluoromethyl, pentafluoroethyl, pentafluorophenyl, and hydrocarbons that are Suitable include dichloromethane, heptafluoronaphthyl. The hydrocarbyl groups of the aryl trichlorome thane, 1,2-dichloroethane, 1-bromo-2- groups are preferably C to Cls alkyl groups or Cs to Cao chloroethane, 1-bromopropane, (chloromethyl) aryl or aralkyl groups. Examples of Suitable hydrocarbyl cyclopropane, 1-bromobutane, 1-bromo-2-ethylbutane, 1,1- groups are methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, 50 dichloro-3,3-dimethylbutane, cyclobutyl chloride, methylcyclohexyl, decyl, phenyl, tolyl, Xylyl, benzyl, neopentyl chloride, 1-bromo-5-chloropentane, cyclopentyl naphthyl, and tetrahydronaphthyl. The alkoxy groups pref bromide, 1-fluorohexane, 1,6-dibromohexane, trans-1,2- erably have C to C alkyl moieties. Some examples of dichlorocyclohexane, 1-chloroheptane, and 1,8- alkoxy groups are methoxy, ethoxy, iSopropoxy, dichlorooctane. Examples of ethers that may be used include methylcyclopentoxy, and cyclohexOxy. The Silyl groups 55 diethyl ether, ethyl n-propyl ether, di-n-propyl ether, diiso preferably have C to Cs alkyl groups or C to Caryl or propyl ether, di-n-butyl ether, tetrahydrofuran, aralkyl groupS. Suitable Silyl groups include trimethylsilyl, methyltetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, cyclo triisopropylsilyl, tert-butyl(dimethyl)silyl, tridecylsilyl, and hexylmethyl ether, glyme (the dimethyl ether of ethylene triphenylsilyl. Examples of aryl groups that may be present glycol), diglyme (the dimethyl ether of diethylene glycol), on the borate moiety in this invention include 3,5-bis 60 triglyme, and tetraglyme. Preferred as the liquid organic (trifluoromethyl)phenyl, 2,4,6-tris(trifluoromethyl)-phenyl, Solvent are Saturated hydrocarbons, particularly those con 4-tri(isopropyl)silyl)-tetrafluorophenyl, 4-dimethyl(tert taining up to about ten carbon atoms. Also preferred are butyl)silyl)-tetrafluorophenyl, 4'-(methoxy)- liquid aromatic hydrocarbons, particularly preferred is tolu octafluorobiphenylyl, 2,3-bis(pentafluoroethyl)-naphthyl, ene. Preferably, the liquid organic Solvent is dry, and it is 2-(isoprop oxy)-hexafluoro naphthyl, 9,10-bis 65 preferred that the reaction is conducted in an inert atmo (heptafluoropropyl)-heptafluoroanthryl, 9,10-bis(p-tolyl)- Sphere comprised of one or more inert gases, Such as, for heptafluorophenanthryl, and 1-(trifluoromethyl)- example, nitrogen, helium, or argon. US 6,169,208 B1 S 6 The term “triarylmethyl cation” refers to carbocations element of any of Groups 15-17 of the Periodic Table, each which have three aryl groups bound to a central carbon R is independently a hydrocarbyl group containing up to atom. The aryl groups of the triarylmethyl cation have from about thirty carbon atoms, and n is equal to the Valence of Six to about twenty carbon atoms, can be the same or E plus one. R is preferably an aliphatic or aromatic hydro different, and can be Substituted or unsubstituted. Examples carbyl group. AS an example of n, when E is Sulfur, which of Suitable aryl groups include phenyl, tolyl, Xylyl, naphthyl, has a Valence of two, n is three. AS described previously for and 2-ethylnaphthyl, preferred are tolyl and phenyl; most both the triarylmethyl Salts and the protic ammonium Salts, preferred is phenyl. The most preferred triarylmethyl cation many inorganic anions may be appropriate counterions for is a triphenylmethyl cation. the onium cation. Preferred inorganic anions are the halides, especially chloride; thus, the preferred Salt is generally an Many inorganic anions can be appropriate counterions for onium chloride. To form the onium tetrakis(aryl)borates, a triarylmethyl cation; examples of Suitable inorganic anions Standard cation exchange methods can be used. Choice(s) of include chloride, bromide, iodide, tetrafluoroborate, Solvent and temperature will vary with the particular System hexafluorophosphate, and the like. Preferred inorganic of onium salt and tetrakis(aryl)borate chosen. Examples of anions are the halides, especially chloride; thus, the pre Suitable onium Salts include, but are not limited to, diphe ferred salt is triphenylmethyl chloride. 15 nyliodonium chloride, tris(p-tolyl)sulfonium bromide, and The magnesium ditetrakis(aryl)borate) can be com tetraethylphosphonium chloride. bined with the triarylmethyl salt and the liquid medium in Generally, the magnesium ditetrakis(aryl)borate) and any order. Mixing of magnesium ditetrakis(aryl)borate) the triarylmethyl Salt, protic ammonium Salt, or onium Salt with the triarylmethyl salt prior to the addition of the liquid are mixed together at room temperature. Mixing at room medium may cause the formation of a cake. Thus, it is temperature is preferred because the yield of triarylmethyl, preferred that both the liquid medium and the triarylmethyl protic ammonium, or onium tetrakis(aryl)borate is often Salt are present in the reaction vessel before the magnesium much higher than when the mixture is heated. Some heat ditetrakis(aryl)borate) is added. may be produced during the course of the reaction, raising Protic ammonium salts of the tetrakis(aryl)borate can be 25 the temperature of the mixture. The mixture may be heated, formed from the magnesium ditetrakis(aryl)borate). These provided that the temperature does not exceed the thermal ammonium cations have the general formula RNH6B, decomposition temperature of the product of the reaction. wherein each R is independently a hydrocarbyl group con Heating during contacting of magnesium ditetrakis(aryl) taining up to about thirty carbon atoms. R is preferably an borate and the triarylmethyl, protic ammonium, or onium aliphatic or aromatic hydrocarbyl group; preferred hydro Salt is preferred when a faster reaction rate is desired. carbyl groups include methyl and phenyl. Examples of Agitation of the reaction mixture is usually necessary for the Suitable protic ammonium cations include, but are not lim reaction to proceed. ited to, trimethylammonium, triethylammonium, cyclohexyl The contact time for magnesium ditetrakis(aryl)borate) (dimethyl)ammonium, tri(n-octyl)ammonium, phenyl and the protic ammonium Salt or onium Salt is preferably (dimethyl)ammonium, diphenyl(ethyl)ammonium, and 35 from about fifteen minutes to about eight hours; more triphenylammonium cations. AS described above for the preferred is a time in the range of from about forty-five triarylmethyl Salt, many inorganic anions can be appropriate minutes to about Six hours. For mixing the magnesium counterions for the protic ammonium cation. Again, the ditetrakis(aryl)borate) and the triarylmethyl salt, the con halides, especially chloride, are preferred inorganic anions, tact time at room temperature is preferably in the range of thus, the preferred Salt is generally a protic ammonium 40 from about two hours to about thirty hours, and more chloride. preferably is in the range of from about ten hours to about The protic ammonium salt can be formed shortly before twenty-four hours. A contact time for magnesium ditetrakis reacting it with the magnesium ditetrakis(aryl)borate); this (aryl)borate) and the triarylmethyl salt when heating in the is accomplished by reacting RN, wherein R is defined as for range of from about thirty minutes to about twenty hours is the protic ammonium cations, with a protic acid to form the 45 preferred; a more preferable range is from about one hour to protic ammonium cation. Preferred protic acids include about fifteen hours, highly preferred is a contact time in the hydrochloric acid, hydrobromic acid, hydroiodic acid, flu range of from about two hours to about twelve hours. oboric acid, and hexafluorophosphoric acid; hydrochloric From the magnesium ditetrakis(aryl)borate), a large acid is a particularly preferred protic acid. Preferably, the variety of metal salts of the tetrakis(aryl)borate anion may protic ammonium cation is formed in aqueous Solution. 50 be produced from metal salts. The metal cation of the metal The liquid medium for contacting the protic ammonium Salt may be an alkali metal cation, an alkaline earth cation salt and magnesium ditetrakis(aryl)borate) can be any of a other than magnesium, or a transition metal cation. large variety of Solvents, So long as they do not interfere with Examples of transition metal cations include Silver, copper, or decompose the desired reaction products. The exclusion gold, Zinc, iron, palladium, nickel, and cobalt. Monovalent of water is not necessary. When water is at least a part of the 55 cations, Such as alkali metal cations, silver(I), and copper(I), liquid mixture, the aqueous portion is preferably provided are preferred. Alkali metal cations are especially preferred by the freshly-made protic ammonium salt solution. When because these Salts can easily be dried, a useful feature when ether is at least a part of the liquid medium, it may be Subsequent reactions and uses of the metal tetrakis(aryl) provided by the alkali metal tetrakis(aryl)borate solution. borate require a dry Salt. The most preferred alkali metal In Such a case, though it is not considered practical to do So, 60 cations are Sodium and potassium. the alkali metal tetrakis( aryl)borate may be isolated from Suitable anions for the metal Salts are almost limitleSS. the ethereal phase in which it was made and dissolved in Examples of Such anions include, but are not limited to, fresh ether. bicarbonate, carbonate, nitrite, nitrate, phosphate, Sulfite, Other Salts, generally referred to as onium Salts, can be Sulfate, carboxylic acid anions (e.g., acetate, citrate, formate, reacted with the magnesium ditetrakis(aryl)borate) to 65 oxalate, propionate, tartrate, etc.), fluoride, chloride, yield the corresponding onium tetrakis(aryl)borate. Onium bromide, iodide, tetrafluoroborate, and hexafluorophos cations are defined by the formula ER,69, wherein E is an phate. Preferred anions are Sulfate, bicarbonate, and carbon US 6,169,208 B1 7 8 ate, carbonate is particularly preferred. The most preferred other species, it is possible to obtain very pure tetrakis(aryl) metal Salts are thus Sodium carbonate and potassium car borate Salts using liquid clathrate formation as a purification bonate. The metal Salt may be combined with the magne method. sium ditetrakis(aryl)borate in solid form or as a solution; The following examples are presented for purposes of a Solution of the metal Salt, particularly an aqueous Solution, is preferred. illustration, and are not intended to impose limitations on the The amount of metal salt needed for reaction with the Scope of this invention. In Examples 1, 2, and 4–7, bromo magnesium ditetrakis(aryl)borate) can vary with the oxi magnesium tetrakis(pentafluorophenyl)borate was obtained dation State of the metal cation. The use of less than about via a Grignard Synthesis route. one mole of positive charge per about one mole of tetrakis (aryl)borate anion may result in incomplete exchange of EXAMPLE 1. the magnesium for the desired metal cation. Complete Synthesis of (CH5)(CH)NHIB(CFs).via Mg eXchange is generally preferred, So at least about one mole of positive charge per about one mole of tetrakis(aryl) B(C6F5). borate is preferable. More preferred is the use of slightly 15 20.0 g of a 20.77 wt % solution of BrMgB(CF). (4.15 more than about one mole of positive charge per about one g, 5.3 mmol) in diethyl ether is added to 20.0 g of HO at mole of tetrakis(aryl)borate anion. Thus, it is preferable to 25 C. during 15 minutes. The resultant two-layer mixture is use at least about two moles of positive charge per mole of stirred for one hour at 25 C. The lower liquid layer is then magnesium ditetrakis(aryl)borate). For example, the use removed, yielding 16.4 g of ethereal solution. 2.91 mmol of of at least about one mole of potassium carbonate per mole Mg is present in the ethereal solution, as determined by ICP, of magnesium ditetrakis(aryl)borate) is preferred, while at and all of the B(CF)le is in the ethereal solution, as least about two moles of Silver nitrate per mole of magne determined by 'F NMR. sium ditetrakis(aryl)borate) are preferable. 0.277 g (2.27 mmol) of (CH)N(CH) and 0.554 g of 16 For Syntheses of protic ammonium, onium, and triarylm wt.% aqueous HCl (0.089 g, 2.43 mmol) are mixed, forming ethyl salts of tetrakis(aryl)borate from metal tetrakis(aryl) 25 (CH4)(CH)NHICl. 0.554 g of HO is added to the borate Salts, the reaction considerations and conditions are mixture. 5.0 g of the 22.3 wt % MgB(C.F.) (1.10g, 0.80 much the same as described above for the reactions of mmol) solution in diethyl ether is added to the (CH4)(CH) magnesium di(tetrakis(aryl)borate) to form protic NHCl mixture with stirring. This mixture is stirred for two ammonium, onium, and triarylmethyl salts. hours at 25 C. The ethereal and aqueous phases are then Tetrakis(aryl)borate Salts, including protic ammonium Separated, the aqueous phase is washed with 2 g of diethyl Salts in which the protic ammonium cation is without aryl ether, the two layerS obtained are separated, and the ether groups, onium Salts, and triarylmethyl Salts can form liquid Washing is added to the original ethereal phase. The ethereal clathrates in combination with at least one liquid aromatic phase is then washed twice, each time with 1 g of HO. The hydrocarbon. Suitable liquid aromatic hydrocarbons yield of (CH)(CH)NHIB(CF) is 86-89%, as deter include, for example, benzene, toluene, Xylenes, mesitylene, 35 mined by H and 'F NMR. cumene, cymene, and indene. Toluene is the most preferred liquid aromatic hydrocarbon. A weight ratio of tetrakis EXAMPLE 2 (aryl)borate Salt to aromatic hydrocarbon in the range of Synthesis of (CH5)(CH)NMIB(CFs), via Mg from about 1:1.0 to about 1:3.0 is usually effective to form B(C6F5). a stable clathrate, although it is recognized that this ratio 40 may vary Somewhat with the specific cation, tetrakis(aryl) 40.0 g of a 12.78 wt % solution of BrMgB(C.F.) (5.11 borate anion, aromatic hydrocarbon and temperature chosen. g, 6.53 mmol) in diethyl ether is added to 40.0 g of HO at ExceSS aromatic hydrocarbon does not adversely affect the 25-35 C. during 10 minutes. The resultant two-layer mix formation of the liquid clathrate, and a quantity in excess of ture is stirred for 30 minutes and then allowed to stand for the amount that is necessary to form the liquid clathrate is 45 30 minutes. The lower liquid layer is then removed. The preferably used. The addition of heat is Sometimes necessary MgB(CFs) is in the upper ethereal layer. to induce clathrate formation; in Such cases, it is preferred to 1.27 g (10.45 mmol) of (CH)N(CH) and 2.68 g of 16 heat to a temperature below the boiling point of the chosen wt.% aqueous HCl (0.43 g, 11.75 mmol) are mixed, forming liquid aromatic hydrocarbon(s). Liquid clathrates that form (CH4)(CH)NHICl. 3 g of HO is added to the mixture. at ambient temperatures (15 to 30° C.) are highly preferred. 50 The MgB(CFs) solution in diethyl ether is added to the The pressure during clathrate formation is typically atmo (CHS) (CH)NHCl mixture at 25°C. with stirring during Spheric. These clathrates are generally stable when heated, 10 minutes. This mixture is stirred for two hours at 25 C., up to a deformation temperature, Such temperature varying and then allowed to stand for 20 minutes. The ethereal and with the particular cation, anion, and Solvent chosen. aqueous phases are then Separated, and the ethereal phase is The liquid clathrate is generally formed by mixing the 55 washed with two separate 6.0 g portions of HO, which are liquid aromatic hydrocarbon with the tetrakis(aryl)borate each separated from the ether layer. The diethyl ether is then Salt while agitating, until a readily recoverable liquid clath removed at 22–30° C. under a partial vacuum, yielding 10.0 rate layer, immiscible with the liquid aromatic hydrocarbon, g of Solid. 30.0 g of toluene are added to the Solid; remaining is formed. A two-layer mixture is usually formed, and the ether and water, as well as Some toluene, are removed at liquid clathrate is normally the lower layer. The layers are 60 75-80 C. under a partial vacuum. Another 30.0 g of toluene easily Separable, for example by decantation. Once are added, and the mixture is again Subjected to a partial Separated, the addition of exceSS nonsolvent, Such as a vacuum at 75-80 C. to remove toluene. The resultant Solids nonaromatic hydrocarbon, or removal of the aromatic are dissolved by adding 30.0 g of CHCla. 15.0 g of pentane hydrocarbon comprising the liquid clathrate from the liquid are then added to the CH2Cl Solution, precipitating (CHS) clathrate layer by methods Such as vacuum distillation, 65 (CH)NHIB(CF). The solid was collected by filtration usually results in the isolation of the tetrakis(aryl)borate and washed with 15.0 g of pentane. The solid is then dried Salt as a Solid. Because the liquid clathrate layer excludes at 25 C. in vacuo to yield 4.80 g of solid, an isolatedyield US 6,169,208 B1 9 10 of 91.95%. The purity of the (CH) (CH)NHIB(CF). ethereal layer, yielding an oil. 75 g of toluene is added to the is 98%, as determined by H and 'F NMR. oil and then distilled at 59 C. in a partial vacuum, yielding 8.19 g of solid MgB(CFs), an isolated yield of 94.8%. EXAMPLE 3 The solid has a purity of 96.2%, and H NMR indicates that the MgB(C6F5) may be a hydrate. The Solid contains 4 Synthesis of (CH) CIB(CF) from MgB mol % Br, as determined by XRF, and the Mg:B ratio is (C6F5)42 1:2.07, as determined by ICP. 0.783 g of MgB(C.F.) (0.565 mmol) and 15.0 g of Solid MgB(CFS) is added to a solution of KHCO in toluene are mixed at 25 C. 0.39 g of (CH3)CCI(1.4 mmol) HO at 25 C. with stirring during 15 minutes. A white is added to the MgB(C6F5)/toluene mixture with Stirring precipitate, Mg(HCO), and two layers, consisting of an at 25 C. A red (CH) CIB(CF)/toluene liquid clath upper ethereal layer, which contains KB(C6F5), and an rate is observed. This mixture is stirred at 25 C. for aqueous bottom layer, are formed. twenty-four hours under nitrogen, forming a precipitate and Repeating the above procedure using NaHCO in place of two layers, consisting of an upper toluene layer and the red KHCO yielded analogous results. (CH3)CB(CFs)/toluene liquid clathrat bottom layer, 15 are formed. The mixture is filtered to remove the precipitate, EXAMPLE 6 which is washed with 5 g of toluene and then with 10 g of Synthesis of KB(CF) via MgB(CFs). hexane. The upper layer is separated from the red clathrate layer, and 5 g of hexane are added to the Separated red 40.0 g of a 20.77 wt % solution of BrMgB(CF) (8.30 clathrate layer to precipitate the (CH) CIB(CFs). The g, 10.6 mmol) in diethyl ether is added to 40.0 g of HO at solid (CH3)CIB(C6F5) is collected by filtration, 25-35 C. with stirring during 30 minutes. The resultant two washed with 5 g of hexane and dried, yielding 0.93 g of layers are separated, and the ethereal layer containing MgB (CH3)4CIB(CF)), an isolated yield of 85%. 49 ppm of (CF) is added to a solution of KF (1.80 g, 30.8 mmol) magnesium are present, as determined by ICP. The purity of in 25 g of H2O at 25-35 C. with stirring during 30 minutes. 25 The resultant two layers are Separated, and the upper ethe the (CH),CIB(CF) is 96.8-98.3%, as determined by real layer is washed with 5.0 g of HO. The resultant two and 'F NMR layers are separated, and the ether is removed from the EXAMPLE 4 ethereal layer, which contains KB(CF)). 95 g of toluene are added to the Solid KIB(C6F5), and the toluene is then Synthesis of NaB(CFs) via MgB(CFs). distilled at 67-83 C. in a partial vacuum to remove residual water and diethyl ether. The solid obtained is washed with 30 20.0 g of a 20.77 wt % solution of BrMgB(CF). (4.15 g of toluene, and then with 40 g of pentane. The Solid g, 5.3 mmol) in diethyl ether is added to a mixture of 20.0 KB(CF) is dried in vacuo at 2520 C. yielding 6.9 g of g of HO and 20.0 g of diethyl ether at 25–35° C. with KIB(CFS) for an isolated yield of 90.7%. The K:Mg ratio Stirring during 30 minutes. The resultant two layers are 35 in the solid is 265:1, as determined by ICP. The purity of the Separated, and the ethereal layer containing MgB(C6F5). KB(CF) is 98.5% as determined by ICP, and 97.3% as is added to a solution of NaF (0.44g, 10.6 mmol) in 200 g determined by NMR. of HO at 25 C. with stirring during 30 minutes. The resultant two-layer mixture is stirred for one hour at 25 C., EXAMPLE 7 and then allowed to Stand for two hours. A rag is observed 40 Synthesis of KB(CF) via MgB(CF). between the two layers. The lower aqueous layer is removed and washed with 20.0 g of diethyl ether; the resultant two 40.0 g of a 20.77 wt % solution of BrMgB(CF) (8.30 layers are separated, and the upper ethereal wash layer is g, 10.6 mmol) in diethyl ether is added to 40.0 g of HO at combined with the original ethereal layer. The combined 25-35 C. with stirring during 30 minutes. A two-phase ether solution is washed with 10.0 g of HO; the resultant 45 mixture is obtained, and the lower aqueous layer is removed two layers are separated, and the ether layer is added to and washed with 20.0 g of diethyl ether. The ether washing boiling toluene (110° C), and the ether and the water are is combined with the original ethereal layer, which contains distilled. The remaining liquid is cooled to 25 C. 40 g of MgB(C6F5), and the combined ether Solution is added to pentane are added to precipitate the NaB(C6F5). The a solution of KCO (1.83 g 13.3 mmol) in 20.0 g of H2O liquids are decanted, and the Solid NaB(C6F5) is heated in 50 at 25-35 C. with stirring during 30 minutes. The resultant vacuo at 25° C.; the yield of solid NaB(CF) is 93.8%. two layers are separated, and the upper ethereal layer is The Na:Mg ratio in the solid is 70:1, as determined by ICP. washed with 5.0 g of HO. Again, the resultant two layers The purity of the NaB(CF) is 95.6% by ICP, and 96.0% are Separated, and the ether is then removed from the by NMR. The NaB(CF) contains traces of water and Separated ethereal layer, which contains KB(CFs). 93 g diethyl ether. of toluene are added to the solid KIB(CF)), and the 55 toluene is then distilled at 77 C. in a partial vacuum. The EXAMPLE 5 solid KIB(CF) is dried in vacuo at 83° C. for one hour, yielding 7.6 g of KB(C6F5) for a quantitative isolated Synthesis of KB(CF) via MgB(CF). yield. The purity of the KIB(CF) is 93%, as determined by NMR; it contains traces of fluorinated impurities, 40.0 g of a 20.77 wt % solution of BrMgB(CF) (8.30 60 g, 10.6 mmol) in diethyl ether is added to 40.0 g of HO at toluene, diethyl ether, and water. 25-35 C. with stirring during 30 minutes. The resultant two EXAMPLE 8 layers are separated, and the ethereal layer containing MgB (CFS) is washed with 40.0 g of H2O. Because the phase Synthesis of (CH),CIB(CF) from boundary in the resultant two-layer mixture is unclear, a total 65 KIB(CFs). of 40.0 g of diethyl ether are added to the mixture. The two 0.718g of KIB(CFS) (1 mmol) from Example 6 and 30 layers are then Separated, and the ether is removed from the g of toluene are charged to a flask, and about two thirds of US 6,169,208 B1 11 12 the toluene are distilled under nitrogen at 60-110° C. 0.363 Accordingly, even though the claims hereinafter may refer to g (1.3 mmol) of (CH),CC1 is added to the KIB(CF)/ Substances, components and/or ingredients in the present toluene Slurry during five minutes, forming a red-orange tense ("comprises”, “is”, etc.), the reference is to the slurry. The mixture is stirred for twenty-four hours under Substance, component or ingredient as it existed at the time nitrogen, forming a red (CHS)-CIB(C6F5)/toluene liq 5 just before it was first contacted, blended or mixed with one uid clathrate bottom layer, a toluene upper layer, and a KCl or more other Substances, components and/or ingredients in precipitate. The mixture is filtered to collect the solid KCl; accordance with the present disclosure. Whatever transformations, if any, that occur in Situ as a reaction is the KCl is washed with 3.0 g of toluene. The upper toluene conducted is what the claim is intended to cover. Thus the layer is separated from the lower clathrate layer, and 20 g of fact that a Substance, component or ingredient may have lost hexane are added to the Separated clathrate layer to precipi its original identity through a chemical reaction or transfor tate the (CH3)CIB(CFs). The solid (CH3)4CIB mation during the course of contacting, blending or mixing (CFS) is collected by filtration and washed with 4 g of operations, if conducted in accordance with this disclosure hexane. The isolated yield of (CH3)CIB(C6F5) is 87% and with the application of common Sense and the ordinary (the first crop of crystals). The purity of (CH),CIB(CF) skill of a chemist, is thus wholly immaterial for an accurate is 98.2%, as determined by 'F NMR, an 96.9% as 15 understanding and appreciation of the true meaning and determined by H NMR. Substance of this disclosure and the claims thereof. Each and every patent or other publication referred to in EXAMPLE 9 any portion of this Specification is incorporated in toto into this disclosure by reference, as if fully set forth herein. Synthesis of (n-octyl)-NHIB(CF) from KB This invention is Susceptible to considerable variation in (CFs). its practice. Therefore the foregoing description is not 6.3 g of diethyl ether and 0.71 g of (n-octyl)-N (2 mmol) intended to limit, and should not be construed as limiting, are mixed. 1.61 g of ethereal HCl (1 molar, 2.2 mmol) is the invention to the particular exemplifications presented added to the mixture with Stirring during ten minutes, hereinabove. Rather, what is intended to be covered is as set 25 forth in the ensuing claims and the equivalents thereof forming (n-octyl)-NHICl. 1.48g of KB(C.F.) (2 mmol) permitted as a matter of law. are then added to the (n-octyl)-NHCl mixture. The mixture What is claimed is: is stirred at 25 C. for three hours, and then filtered to 1. A proceSS which comprises contacting remove solid KCl. The ether is evaporated from the (n- octyl)-NHIB(C6F5), yielding an oil. 30 g of toluene are i) a Solution comprising a liquid organic medium and a added to the oil at 25 C., forming a liquid clathrate; the halomagnesium tetrakis(aryl)borate, wherein the liquid toluene is then distilled at 50-80 C. in a partial vacuum, organic medium is comprised of one or more liquid again yielding an oil. The oil is further dried in vacuo at 80 dihydrocarbyl ethers, one or more liquid hydrocarbons, C., yielding a Solid. The Solid is washed with pentane, and one or more liquid halogenated hydrocarbons, or mix the pentane is decanted. The Solid is dried at 25 C., again tures thereof, and wherein each of the aryl groups is a in vacuo, yielding 1.5 g of (n-octyl)-NHB(C6F5), an 35 fluorine-containing aryl group, each of which has isolated yield of 75%. The purity of the ether-free (n-octyl) bonded directly to an aromatic ring at least two fluorine NHIB(CF) is 98+2%, as determined by H and 'F atoms, or at least two perfluorohydrocarbyl groups, or NMR. One part of the ether-free (n-octyl)-NHIB(CFs). at least one fluorine atom and at least one perfluoro is added to 8 parts (by weight) of toluene at 25°C.; a bottom hydrocarbyl group, and 40 ii) water, to produce magnesium ditetrakis(aryl)borate oily layer is observed. in the organic phase of a two-phase water/liquid EXAMPLE 10 organic medium. 2. A process according to claim 1 wherein the liquid Synthesis of PhIIB(CF) from NaB(CFs). organic medium is a liquid dihydrocarbyl ether. 45 3. A process according to claim 2 wherein the liquid 0.234 g of NaB(C.F.) (0.33 mmol) from Example 4, dihydrocarbyl ether is diethyl ether. further dried via a toluene azeotrope at 110° C., and 0.105 4. A proceSS according to claim 1 wherein the amount of g of PhIC (0.33 mmol) are stirred at 25–35° C. for 30 water used is about 0.2 to about 3 parts by volume of water minutes. An orange bottom liquid clathrate layer and a clear per part by Volume of liquid organic medium. upper layer are observed. NaCl precipitated, coating the wall 50 5. A process according to claim 1 wherein the halomag of the reaction flask. nesium moiety is a bromomagnesium moiety. It is to be understood that the reactants and components 6. A process according to claim 1 wherein the aromatic referred to by chemical name or formula anywhere in the ring of Said aryl group is a phenyl ring. Specification or claims hereof, whether referred to in the 7. A process according to claim 1 wherein all of the Singular or plural, are identified as they exist prior to coming 55 positions on said aromatic ring(s) of said aryl group are into contact with another Substance referred to by chemical substituted by fluorine atoms. name or chemical type (e.g., another reactant, a Solvent, or 8. A proceSS according to claim 7 wherein the tetrakis etc.). It matters not what preliminary chemical changes, (aryl)borate is tetrakis(pentafluorophenyl)borate. transformations and/or reactions, if any, take place in the 9. A process according to claim 8 wherein the halomag resulting mixture or Solution or reaction medium as Such 60 nesium tetrakis(aryl)borate is bromomagnesium tetrakis changes, transformations and/or reactions are the natural (pentafluorophenyl)borate. result of bringing the Specified reactants and/or components 10. A process according to claim 1 wherein at least a together under the conditions called for pursuant to this portion of the Solution of magnesium ditetrakis(aryl)borate disclosure. Thus the reactants and components are identified in the organic phase is Separated from the aqueous phase. as ingredients to be brought together in connection with 65 11. A process according to claim 10 wherein the magne performing a desired chemical reaction or in forming a sium ditetrakis(aryl)borate is isolated from said Solution of mixture to be used in conducting a desired reaction. magnesium ditetrakis(aryl)borate in the organic phase. US 6,169,208 B1 13 14 12. A proceSS according to claim 1 wherein Said liquid 35. A process according to claim 1 further comprising organic medium comprises diethyl ether, and wherein at mixing, in a liquid medium, at least a portion of Said least a portion of the Solution of magnesium ditetrakis(aryl) magnesium ditetrakis(aryl)borate and at least one metal borate in the organic phase is separated from the aqueous Salt, to produce a metal tetrakis(aryl)borate. phase. 36. A proceSS according to claim 35 wherein Said liquid 13. A process according to claim 1 wherein i) and ii) are medium comprises water. at room temperature when mixed together. 37. A process according to claim 35 wherein the liquid 14. A process according to claim 1 further comprising medium comprises a liquid dihydrocarbyl ether. mixing, in a liquid medium, at least a portion of Said 38. A process according to claim 35 wherein said metal magnesium ditetrakis(aryl)borate and a salt Selected from Salt is an alkali metal Salt. a) a protic ammonium salt, wherein the protic ammonium 39. A process according to claim 38 wherein said alkali cation has the formula RNHée, in which each R is metal Salt is an alkali metal carbonate. independently a hydrocarbyl group containing up to 40. A process according to claim 39 wherein said alkali about thirty carbon atoms, metal carbonate is Sodium carbonate or potassium carbon b) an onium salt, wherein the onium cation has the 15 ate. formula ER, GD, wherein E is an element of any of 41. A process according to claim 40 wherein Said liquid Groups 15-17 of the Periodic Table, wherein each R is medium comprises water and a liquid dihydrocarbyl ether. independently a hydrocarbyl group containing up to 42. A proceSS according to claim 35 further comprising about thirty carbon atoms, and wherein n is equal to the Valence of E plus one, and mixing, in a liquid medium, at least a portion of the metal c) a triarylmethyl salt, wherein the triarylmethyl cation tetrakis(aryl)borate and a Salt Selected from has three aryl groupS bound to a central carbon atom, a) a protic ammonium salt, wherein the protic ammonium to produce a protic ammonium tetrakis(aryl)borate, an cation has the formula RNHCB, in which each R is onium tetrakis(aryl)borate, or a triarylmethyl tetrakis independently a hydrocarbyl group containing up to (aryl)borate. about thirty carbon atoms, 15. A process according to claim 14 wherein Said Salt is 25 b) an onium salt, wherein the onium cation has the a protic ammonium Salt or an onium Salt, and wherein the formula ER6D, wherein E is an element of any of liquid medium comprises water. Groups 15-17 of the Periodic Table, wherein each R is 16. A process according to claim 14 wherein the liquid independently a hydrocarbyl group containing up to medium comprises a liquid dihydrocarbyl ether. about thirty carbon atoms, and wherein n is equal to the 17. A process according to claim 14 wherein Said Salt is Valence of E plus one, and a protic ammonium Salt. c) a triarylmethyl salt, wherein the triarylmethyl cation 18. A process according to claim 17 wherein at least one has three aryl groups bound to a central carbon atom, R group of Said protic ammonium cation is a phenyl group. to produce a protic ammonium tetrakis(aryl)borate, an 19. A process according to claim 17 wherein the protic onium tetrakis(aryl)borate, or a triarylmethyl tetrakis ammonium cation is a phenyl(dimethyl)ammonium cation. 35 (aryl)borate. 20. A process according to claim 19 wherein the liquid 43. A process according to claim 42 wherein Said Salt is medium comprises water and a liquid dihydrocarbyl ether. a protic ammonium Salt or an onium Salt, and wherein the 21. A proceSS according to claim 17 wherein the protic liquid medium comprises water. ammonium cation is a tri(n-octyl)ammonium cation. 44. A proceSS according to claim 42 wherein the liquid 22. A proceSS according to claim 21 wherein the liquid 40 medium comprises a liquid dihydrocarbyl ether. medium comprises a liquid dihydrocarbyl ether. 45. A process according to claim 42 wherein Said Salt is 23. A process according to claim 14 wherein Said Salt is a protic ammonium Salt. an onium Salt. 46. A process according to claim 45 wherein at least one 24. A process according to claim 23 wherein at least one R group of Said protic ammonium cation is a phenyl group. R group of Said onium cation is a phenyl group. 45 47. A process according to claim 45 wherein the protic 25. A process according to claim 23 wherein all of the R ammonium cation is a phenyl(dimethyl)ammonium cation. groups of Said onium cation are the Same. 48. A process according to claim 47 wherein the liquid 26. A process according to claim 24 wherein Said onium medium comprises water and a liquid dihydrocarbyl ether. Salt is a diphenyliodonium Salt. 49. A process according to claim 45 wherein the protic 27. A process according to claim 14 wherein Said Salt is 50 ammonium cation is a tri(n-octyl)ammonium cation. a triaryimethyl Salt. 50. A process according to claim 49 wherein the liquid 28. A process according to claim 27 wherein Said liquid medium comprises a liquid dihydrocarbyl ether. medium comprises at least one liquid hydrocarbon. 51. A process according to claim 42 wherein Said Salt is 29. A process according to claim 28 wherein said hydro an onium Salt. carbon is an alkane hydrocarbon or mixture of alkane 55 52. A process according to claim 51 wherein at least one hydrocarbons. R group of Said onium cation is a phenyl group. 30. A process according to claim 28 wherein said liquid 53. A process according to claim 51 wherein all of the R medium comprises at least one liquid aromatic hydrocarbon. groups are the Same. 31. A process according to claim 30 wherein Said liquid 54. A process according to claim 52 wherein Said onium medium comprises toluene. 60 Salt is a diphenyliodonium Salt. 32. A process according to claim 27 wherein at least one 55. A process according to claim 42 wherein Said Salt is aryl group of Said triarylmethyl cation is a phenyl group. a triarylmethyl Salt. 33. A process according to claim 32 wherein the triaryl 56. A process according to claim 55 wherein said liquid methyl cation is a triphenylmethyl cation. medium comprises at least one liquid hydrocarbon. 34. A process according to claim 14 wherein Said at least 65 57. A process according to claim 56 wherein said hydro a portion of magnesium ditetrakis(aryl)borate and said Salt carbon is an alkane hydrocarbon or mixture of alkane are at room temperature when mixed together. hydrocarbons. US 6,169,208 B1 15 16 58. A process according to claim 56 wherein said liquid 61. A process according to claim 60 wherein the triaryl medium comprises at least one liquid aromatic hydrocarbon. methyl cation is a triphenylmethyl cation. 62. A process according to claim 42 wherein Said at least 59. A process according to claim 58 wherein said liquid a portion of metal tetrakis(aryl)borate and Said Salt are at medium comprises toluene. 5 room temperature when mixed together. 60. A process according to claim 55 wherein at least one aryl group of Said triarylmethyl cation is a phenyl group. k . . . .