USING COBALT CATALYSTS

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation-in-part of U.S. Application No. 14/270,710 filed May 6, 2014, which is a continuation-in-part of U.S. Application No. 13/966,568 filed on August 14, 2013, which claims the benefit of Provisional Application No. 61/819,761 filed on May 6, 2013, Provisional Application No. 61/819,753 filed on May 6, 2013, and Provisional Application No. 61/683,882 filed on August 16, 2012. This application also claims the benefit of Provisional Application 61/906,210 filed on November 19, 2013.

FIELD OF THE INVENTION

[0002] This invention relates generally to transition metal-containing compounds, more specifically to cobalt complexes containing pyridine di-imine ligands and their use as efficient dehydrogenative silylation, hydrosilylation and crosslinking catalysts.

BACKGROUND OF THE INVENTION

[0003] Hydrosilylation chemistry, typically involving a reaction between a silyl hydride and an unsaturated organic group, is the basis for synthetic routes to produce commercial silicone-based products like silicone surfactants, silicone fluids and silanes as well as many addition cured products like sealants, adhesives, and silicone-based coating products. See, for example, US Patent Application Publication 2011/0009573 Al to Delis et al. Typical hydrosilylation reactions use precious metal catalysts to catalyze the addition of a silyl-hydride (Si-H) to an unsaturated group, such as an olefin. In these reactions, the resulting product is a silyl-substituted, saturated compound. In most of these cases, the addition of the silyl group proceeds in an anti-Markovnikov manner, i.e., to the less substituted carbon atom of the unsaturated group. Most precious metal catalyzed hydrosilylations only work well with terminally unsaturated olefins, as internal unsaturations are generally non-reactive or only poorly reactive. There are currently only limited methods for the general hydrosilylation of olefins where after the addition of the Si-H group there still remains an unsaturation in the original substrate. This reaction, termed a dehydrogenative silylation, has potential uses in the synthesis of new silicone materials, such as silanes, silicone fluids, crosslinked silicone elastomers, and silylated or silicone-crosslinked organic polymers such as polyolefms, unsaturated polyesters, and the like. [0004] Various precious metal catalysts are known in the art. For example, US Patent No. 3,775,452 discloses a platinum complex containing unsaturated siloxanes as ligands. This type of catalyst is known as Karstedt's catalyst. Other exemplary platinum-based hydrosilylation catalysts that have been described in the literature include Ashby's catalyst as disclosed in US Patent No. 3,159,601, Lamoreaux's catalyst as disclosed in US Patent No. 3,220,972 , and Speier's catalyst as disclosed in Speier, J.L, Webster J.A. and Barnes G.H., J. Am. Chem. Soc. 79, 974 (1957).

[0005] There are examples of the use of Fe(CO) ₅ to promote limited hydrosilylations and dehydrogenative silylations. (See Nesmeyanov, A. N.; Freidlina, R. Kh.; Chukovskaya, E. C; Petrova, R. G.; Belyavsky, A. B. Tetrahedron 1962, 17, 61 and Marciniec, B.; Majchrzak, M. Inorg. Chem. Commun. 2000, 3, 371). The use of Fe ₃ (CO)i ₂ was also found to exhibit dehydrogenative silylation in the reaction of Et ₃ SiH and styrene. (Kakiuchi, F.; Tanaka, Y.; Chatani, N.; Murai, S. J. Organomet.Chem. 1993, 456, 45). Also, several cyclopentadiene iron complexes have been used to varying degrees of success, with the work of Nakazawa, et al showing interesting intramolecular dehydrogenative silylation/hydrogenation when used with 1,3-di- vinyldisiloxanes. (Roman N Naumov, Masumi Itazaki, Masahiro Kamitani, and Hiroshi Nakazawa, Journal of the American Chemical Society, 2012, Volume 1.34, Issue 2, Pages 804-807),

[0006] A rhodium complex was found to give low to moderate yields of allyl-silanes and vinyl silanes. (Doyle, M.P.; Devora G. A.; Nevadov, A. O.; High, K. G. Organometallics, 1992, 11, 540- 555). An iridium complex was also found to give vinyl silanes in good yields. (Falck, J. R.; Lu, B, J. Org Chem, 2010, 75, 1701-1705.) Allyl silanes could be prepared in high yields using a rhodium complex (Mitsudo, T.; Watanabe, Y.; Hori, Y. Bull. Chem. Soc. Jpn. 1988, 61, 3011-3013). Vinyl silanes could be prepared through the use of a rhodium catalyst (Murai, S.; Kakiuchi, F.; Nogami, K.; Chatani, N.; Seki, Y. Organometallics, 1993, 12, 4748-4750). Dehydrogenative silylation was found to occur when iridium complexes were used (Oro, L. A.; Fernandez, M. J.; Esteruelas, M. A.; Jiminez, M. S. J. Mol. Catalysis, 1986, 37, 151-156 and Oro, L. A.; Fernandez, M. J.; Esteruelas, M. A.; Jiminez, M. S. Organometallics, 1986, 5, 1519-1520). Vinyl silanes could also be produced using ruthenium complexes (Murai, S.; Seki, Y.; Takeshita, K.; Kawamoto, K.; Sonoda, N. J. Org. Chem. 1986, 51, 3890-3895.).

[0007] A palladium-catalyzed silyl-Heck reaction was recently reported to result in the formation of allyl-silanes and vinyl silanes (McAtee JR, et al., Angewandte Chemie, International Edition in English (March 1, 2012); McAtee, JR et al, J. Am. Chem. Soc. 2014, 136, 10166).

[0008] US Patent No. 5,955,555 discloses the synthesis of certain iron or cobalt pyridine di-imine (PD1) complexes bearing two ionic ligands. The preferred anions are chloride, bromide and tetrafluoroborate. US Patent No. 7,442,819 discloses iron and cobalt complexes of certain tricyclic ligands containing a "pyridine" ring substituted with two imino groups. US Patent Nos. 6,461,994, 6,657,026 and 7,148,304 disclose several catalyst systems containing certain transitional metal-PDI complexes. US Patent No. 7,053,020 discloses a catalyst system containing, inter alia, one or more bisarylimino pyridine iron or cobalt catalyst. Chirik et al describe bisarylimino pyridine cobalt complexes with anionic ligands (Inorg. Chem. 2010, 49, 6110 and JACS. 2010, 132, 1676.) However, the catalysts and catalyst systems disclosed in these references are described for use in the context of olefin hydrogenation, polymerizations and/or oligomerisations, not in the context of dehydrogenative silylation reactions. Pyridine(di)imine cobalt methyl complexes with N-alkyl substituents have been reported to give mixtures of hydrosilylation and dehydrogenative silylation products when reacted with silylhydrides and excess olefin (Atienza, C. C. H. A, PhD thesis (2013), Princeton University). Certain derivatives of pyridine(di)imine cobalt methyl complexes with N- alkyl substituents have proven challenging to synthesize thus necessitating the production of pre- catalysts such as pyridine(di)imine cobalt neosilyl complexes.

[0009] There is a continuing need in the silylation industry for non-precious metal-based catalysts that are effective for efficiently catalyzing dehydrogenative silylations and/or hydrosilylation. The present invention provides one answer to that need.

[0010] Further, many industrially important homogeneous metal catalysts suffer from the drawback that following consumption of the first charge of substrates, the catalytically active metal is lost to aggregation and agglomeration whereby its catalytic properties are substantially diminished via colloid formation or precipitation. This is a costly loss, especially for noble metals such as Pt. Heterogeneous catalysts are used to alleviate this problem but have limited use for polymers and also have lower activity than homogeneous counterparts. For example, it is well-known in the art and in the hydrosilylation industry that the two primary homogeneous catalysts, Speier's and Karstedt's, often lose activity after catalyzing a charge of olefin and silyl- or siloxyhydride reaction. If one charge of the homogeneous catalyst could be re-used for multiple charges of substrates, then catalyst and process cost advantages would be significant.

SUMMARY OF THE INVENTION

[0011] In one aspect, the present invention is directed to a process for producing a silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, to produce a dehydrogenative silylated product, a hydrosilylated product, or a combination of a dehydrogenative silylated product and a hydrosilylated product, wherein the catalyst is a complex of the Formula (I) or an adduct thereof;

(I)

wherein each occurrence of R ¹ , R ² , R ³ , R ⁴ , and R ⁵ is independently hydrogen, a C1-C18 alkyl, a Cl- C18 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, R ^! -R ⁵ , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R ⁶ and R ⁷ is independently a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, an aryl, or a substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom;

optionally any two of R 1, R 2, R 3, R 4, R 5, R 6, and R 1 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and

8 8

L is CH ₂ SiR 3 where each occurrence of R is independently a CI -10 alkyl or an aryl group,

Q

where R optionally contains at least one heteroatom.

Q

[0012] In one embodiment, R is CH ₃ .

[0013] In one embodiment, R ⁶ and R ⁷ are independently chosen from a CI -CIO alkyl. In one embodiment, R ⁶ and R ⁷ are each methyl. In one embodiment, R ⁶ and R ⁷ are each ethyl. In one embodiment, R ⁶ and R ⁷ are each cyclohexyl.

[0014] In one embodiment, R 8 is methyl; R 6 and R 7 are independently chosen from a C1-C10 alkyl,

2 3 4

and R , R , and R are each hydrogen.

[0015] In one embodiment, the catalyst is chosen from:

or a combination of two or more thereof.

[0016] In one embodiment, component (a) is chosen from an olefin, a cycloalkene, an unsaturated polyether, a vinyl-functional alkyl-capped allyl or methallyl polyether, an alkyl-capped terminally unsaturated amine, an alkyne, a terminally unsaturated acrylate or methacrylate, an unsaturated aryl ether, a vinyl-functionalized polymer or oligomer, a vinyl-functionalized silane, a vinyl- functionalized silicone, an unsaturated fatty acid, an unsaturated ester, or a combination of two or more thereof.

[0017] In one embodiment, component (a) is chosen from a compound of the formula:

R ¹⁰ (OCH ₂ CH ₂ ) _Z (OCH ₂ CHR ¹¹ ) _W -OR ¹² ;

R ¹ O(CHR ^u CH ₂ 0) _w (CH ₂ CH ₂ 0) _z -CR ¹ 2-C≡C-CR ¹ ₂ - (OCH ₂ CH ₂ ) _z (OCH ₂ CHR ⁿ ) _w R ¹² ; H ₂ C=CR ¹¹ CH ₂ 0(CH ₂ CH ₂ 0) _z (CH ₂ CHR ¹¹ ) _w CH ₂ CR ¹ =CH ₂ ; or a combination of two or more thereof, wherein R is chosen from an unsaturated organic group containing from 2 to 10 carbon atoms; R 12 is chosen from hydrogen, a vinyl group, or a polyether capping group of from 1 to 8 carbon atoms; each occurrence of R ¹¹ is independently chosen from a monovalent hydrocarbon group having 1-20 carbon atoms, an aryl group, an alkaryl, an aralkyl, a cycloalkyl group; each occurrence of R 13 is independently chosen from hydrogen, a monovalent hydrocarbon group having 1-20 carbon atoms, an aryl group, an alkaryl group, an aralkyl group, or a cycloalkyl group; each occurrence of z is 0 to 100 inclusive; and, each occurrence of w is 0 to 100 inclusive.

[0018] In one embodiment, component (a) is chosen from Ν,Ν-dimethylallyl amine, allyloxy- substituted polyethers, propylene, 1-butene, 1-hexene, styrene,, vinylnorbornane, 5-vinyl- norbornene, 1-octadecene, cyclopentene, cyclohexene, norbornene, 3-hexene, isobutylene, 3- methyl- 1-octene, polybutadiene, polyisoprene, EPDM, oleic acid, linoleic acid, methyl oleate, a vinyl siloxane of the Formula VI,

(VI)

or a combination of two or more thereof, wherein each occurrence of R is independently a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, vinyl, aryl, or a substituted aryl, and n is greater than or equal to zero.

[0019] In one embodiment, component (b) is chosen from a compound of the formula R _a SiH ₄ _ _a; (RO) _a SiH ₄ _ _a , HSiR _a (OR) ₃ _ _a , R ₃ Si(CH ₂ ) _f (SiR ₂ 0) _k SiR ₂ H, (RO) ₃ Si(CH ₂ ) _f (SiR ₂ 0) _k SiR ₂ H, Q _u T _v T _p ^H D _w D ^H _x M ^H _y M _z , R ₃ Si(CH ₂ R) _x SiOSiR ₂ (OSiR ₂ ) _y OSiR ₂ H, or combinations of two or more thereof where each occurrence of R is independently a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, wherein R optionally contains at least one heteroatom, each occurrence of a independently has a value from 0 to 3, f has a value of 1 to 8, k has a value of 1 to 11, each of p, u, v, y and z independently has a value from 0 to 20, w and x are from 0 to 3000, provided that p + x + y equals 1 to 1000 and the valences of the all the elements in the silyl hydride are satisfied, M represents a monofunctional group of formula R' ₃ SiOi _/2 , D represents a difunctional group of formula R' ₂ Si0 _2/2 , T represents a trifunctional group of formula R'Si0 _3/2 , Q represents a tetrafunctional group of formula Si0 _4/2, an M ^H represents HR' ₂ SiOi _/2 , T ^H represents HSi0 _3/2 , and D ^H represents R'HSi0 _2/2 ; each occurrence of R' is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, wherein R' optionally contains at least one heteroatom; x is 1-8, and y is 0-10.

[0020] In one embodiment, the catalyst is present in an amount of from 0.01 mole percent to 10 mole percent based on the molar quantity of the unsaturated compound to be reacted.

[0021] In one embodiment, the process is conducted at a temperature of between about 0 °C and about 300 °C.

[0022] In one embodiment, the complex is immobilized on a support. In one embodiment, the support is chosen from carbon, silica, alumina, MgCl ₂ , zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), sulfonated polystyrene, or a combination of two or more thereof.

[0023] In one aspect, the present invention provides a process for producing a hydrosilylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, in order to produce the dehydrogenative silylated product, and/or hydrosilylated product wherein the catalyst is a complex of the Formula (I) or an adduct thereof;

(I)

wherein each occurrence of R ¹ , R ² , R ³ , R ⁴ , and R ⁵ is independently hydrogen, a C1-C18 alkyl, a Cl- C18 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, wherein R ^! -R ⁵ , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R ⁶ and R ⁷ is independently a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, an aryl, a substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom;

optionally any two of R 1, R 2, R 3, R 4, R 5, R 6, and R 1 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and

L is CH ₂ SiR 8 ₃ where each R 8 is independently a CI -10 alkyl or aryl group optionally containing at least one heteroatom. [0024] In one embodiment, component (a) is chosen from an olefin, a cycloalkene, an alkyl-capped allyl polyether, a vinyl-functional alkyl-capped allyl or methallyl polyether, an alkyl-capped terminally unsaturated amine, an alkyne, a terminally unsaturated acrylate or methacrylate, an unsaturated aryl ether, a vinyl-functionalized polymer or oligomer, a vinyl-functionalized silane, a vinyl-functionalized silicone, an unsaturated fatty acid, an unsaturated ester, or a combination of two or more thereof; and component (b) is chosen from a compound of the formula R _a SiH ₄ _ _a, (RO) _a SiH ₄ _a, HSiR _a (OR) ₃ -a, R ₃ Si(CH ₂ ) _f (SiR ₂ 0) _k SiR ₂ H, (RO) ₃ Si(CH ₂ ) _f (SiR ₂ 0) _k SiR ₂ H, Q _u T _v T _p ^H D _w D ^H _x M ^H _y M _z , R ₃ Si(CH ₂ R) _x SiOSiR ₂ (OSiR ₂ ) _y OSiR ₂ H and combinations of two or more thereof where each occurrence of R is independently a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, wherein R optionally contains at least one heteroatom, each occurrence of a independently has a value from 1 to 3, f has a value of 1 to 8, k has a value of 1 to 11, each of p, u, v, y and z independently has a value from 0 to 20, w and x are from 0 to 500, provided that p + x + y equals 1 to 500 and the valences of the all the elements in the silyl hydride are satisfied, M represents a monofunctional group of formula R' ₃ SiOi _/2 , a D represents a difunctional group of formula R' ₂ Si0 ₂ / ₂ , T represents a trifunctional group of formula R'Si0 ₃ / ₂ , Q represents a tetrafunctional group of formula S1O4/2, an M ^H represents HR' ₂ SiOi/ ₂ , T ^H represents HSi0 ₃ / ₂ , and D ^H represents R'HSi0 _2/2 ; each occurrence of R' is independently a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, wherein R' optionally contains at least one heteroatom.

[0025] In one embodiment, component (a) is chosen from a vinyl-functionalized silane, a vinyl- functionalized silicone, or a combination thereof.

[0026] In one embodiment, com onent (a) is chosen from a vinyl siloxane of the formula

wherein each occurrence of R is independently a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a vinyl, an aryl, a substituted aryl, and n is greater than or equal to zero.

[0027] In one embodiment, R ⁶ and R ⁷ are each methyl.

[0028] In one embodiment, component (b) comprises a trialkoxy silyl hydride.

[0029] In one embodiment, component (a) is chosen from an olefin, a cycloalkene, an alkyl-capped allyl polyether, a vinyl-functional alkyl-capped allyl or methallyl polyether, an alkyl-capped terminally unsaturated amine, an alkyne, a terminally unsaturated acrylate or methacrylate, an unsaturated aryl ether, a vinyl-functionalized polymer or oligomer, a vinyl-functionalized silane, a vinyl-functionalized silicone, an unsaturated fatty acid, an unsaturated ester, or a combination of two or more thereof. [0030] In one embodiment, the catalyst is present in an amount of from 0.01 mole percent to 10 mole percent based on the molar quantity of the unsaturated compound to be reacted.

[0031] In one embodiment, the process is conducted at a temperature of between about 0 °C and about 300 °C.

[0032] In one aspect, the present invention provides a process for producing a crosslinked material, comprising reacting a mixture comprising (a) a silyl-hydride containing polymer, (b) a mono- unsaturated olefin or an unsaturated polyolefm, or combinations thereof and (c) a catalyst, optionally in the presence of a solvent, in order to produce the crosslinked material, wherein the catalyst is a complex of the Formula (I) or an adduct thereof:

wherein each occurrence of R ¹ , dently hydrogen, a C1-C18 alkyl, a Cl- C18 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, wherein R ^! -R ⁵ , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R ⁶ and R ⁷ is independently a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom;

optionally any two of R 1, R 2, R 3, R 4, R 5, R 6, and R 1 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and

L is CH ₂ SiR 8 8

3 where each R is independently a CI -10 alkyl or aryl group optionally containing at least one heteroatom.

[0033] In one embodiment, the reaction is conducted under an inert atmosphere.

[0034] In one embodiment, the reaction is conducted in the presence of a solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, and combinations thereof.

[0035] In one embodiment, the reaction is carried out at a temperature of 0° C. to 300° C.

[0036] In one embodiment, the catalyst is present in an amount of from about 0.1 mol % to about 5 mol %.

DETAILED DESCRIPTION OF THE INVENTION

[0037] The invention relates to cobalt complexes containing pyridine di-imine ligands and their use as efficient dehydrogenative silylation, hydrosilylation, and crosslinking catalysts. In one embodiment of the invention, there is provided a complex of the Formulae (I) or (II), wherein Co may be in any valence or oxidation state (e.g., +1, +2, or +3) for use in said dehydrogenative silylation, hydrosilylation, and crosslinking reactions. In particular, according to one embodiment of the invention, a class of cobalt pyridine di-imine complexes has been found that are capable of dehydrogenative silylation and/or hydrosilylation reactions.

[0038] By "alkyl" herein is meant to include straight, branched and cyclic alkyl groups. Specific and non-limiting examples of alkyls include, but are not limited to, methyl, ethyl, propyl, isobutyl and cyclohexyl.

[0039] By "substituted alkyl" herein is meant an alkyl group that contains one or more substituent groups that are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially or deleteriously interfere with the process.

[0040] By "aryl" herein is meant a non-limiting group of any aromatic hydrocarbon from which one hydrogen atom has been removed. An aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups. Specific and non-limiting examples of aryls include, but are not limited to, tolyl, xylyl, phenyl and naphthalenyl.

[0041] By "substituted aryl" herein is meant an aromatic group substituted as set forth in the above definition of "substituted alkyl." Similar to an aryl, a substituted aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the free valence in the substituted aryl group can be to a heteroatom (such as nitrogen) of the heteroaromatic ring instead of a carbon. If not otherwise stated, it is preferred that substituted aryl groups herein contain 1 to about 30 carbon atoms.

[0042] By "alkenyl" herein is meant any straight, branched, or cyclic alkenyl group containing one or more carbon-carbon double bonds, where the point of substitution can be either a carbon-carbon double bond or elsewhere in the group. Specific and non-limiting examples of alkenyls include, but are not limited to, vinyl, propenyl, allyl, methallyl, ethylidenyl norbornane.

[0043] By "alkynyl" is meant any straight, branched, or cyclic alkynyl group containing one or more carbon-carbon triple bonds, where the point of substitution can be either at a carbon-carbon triple bond or elsewhere in the group.

[0044] By "unsaturated" is meant one or more double or triple bonds. In one embodiment, it refers to carbon-carbon double or triple bonds.

[0045] By "inert substituent" herein is meant a group other than hydrocarbyl or substituted hydrocarbyl, which is inert under the process conditions to which the compound containing the group is subjected. The inert substituents also do not substantially or deleteriously interfere with any process described herein that the compound in which they are present may take part in. Examples of inert substituents include halo (fluoro, chloro, bromo, and iodo), ether such as -OR ⁹ wherein R ⁹ is hydrocarbyl or substituted hydrocarbyl.

[0046] By "hetero atoms" herein is meant any of the Group 13-17 elements except carbon, and can include for example oxygen, nitrogen, silicon, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine.

[0047] By "olefin" herein is meant any aliphatic or aromatic hydrocarbon also containing one or more aliphatic carbon-carbon unsaturations. Such olefins may be linear, branched or cyclic and may be substituted with heteroatoms as described above, with the proviso that the substituents do not interfere substantially or deleteriously with the course of the desired reaction to produce the dehydrogenatively silylated and/or hydrosilylated product. In one embodiment, the unsaturated compound useful as a reactant in the dehydrogenative silylation/hydrosilylation is an organic compound having the structural group, R ₂ C=C-CHR, where R is an organic fragment or hydrogen.

[0048] As indicated above, the present invention is directed to a process for producing a dehydrogenatively silylated and/or hydrosilylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, in order to produce the dehydrogenative silylated product, and/or hydrosilylated product wherein the catalyst is a complex of the Formula (I) or an adduct thereof;

(I)

wherein

each occurrence of R ¹ , R ² , R ³ , R ⁴ , and R ⁵ is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R ^! -R ⁵ , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R ⁶ and R ⁷ is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom; optionally any two of R 1, R 2, R 3, R 4, R 5, R 6 and R 7 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and L hydroxyl, chloride, bromide, or a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl, or substituted aryl group, or component (a) wherein L optionally contains at least one heteroatom.

[0049] In one embodiment, L is CH ₂ SiR 8 ch R 8

3 where ea is independently a CI -10 alkyl or aryl

Q

group optionally containing at least one heteroatom. In one embodiment, R is a methyl group (Me).

[0050] The catalyst utilized in the process of the present invention is illustrated in Formula (I) above wherein Co is in any valence or oxidation state (e.g., +1, +2, or +3). In one embodiment, at least one of R ⁶ and R ⁷ is a CI -CIO alkyl. Examples of suitable groups for R ⁶ and R ⁷ include, but are not limited to, methyl, ethyl, propyl, butyl, or cyclohexyl, etc. Non-limiting examples of suitable compounds include:

[0051] Various methods can be used to prepare the catalyst utilized in the process of the present invention. In one embodiment, the catalyst is generated in-situ by contacting a catalyst precursor with an activator in the presence of a liquid medium containing at least one component selected from the group consisting of a solvent, the silyl hydride, the compound containing at least one unsaturated group, and combinations thereof, wherein the catalyst precursor is represented by structural Formula II

(Π)

wherein

each occurrence of R ¹ , R ² , R ³ , R ⁴ , and R ⁵ is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R ^! -R ⁵ , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R ⁶ and R ⁷ is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom;

optionally any two of R 1, R 2, R 3, R 4, R 5, R 6 and R 1 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and

X is an anion selected from the group consisting of F ^" , CI ^" , Br ^" , Γ, CF ₃ R ⁴⁰ SO ₃ ^" or R ⁵⁰ COO ^" , wherein R ⁴⁰ is a covalent bond or a C1-C6 alkylene group, and R ⁵⁰ is a CI -CIO hydrocarbyl group.

Q

[0052] The activator is an alkali metal alkyl of the formula MCH ₂ SiR 3, where M is an alkali metal.

[0053] The methods to prepare the catalysts are known to a person skilled in the field. For example, the catalysts can be prepared by reacting a PDI ligand with a metal halide, such as CoCl ₂ as disclosed in US Patent Application Publication 2011/0009573A1. Typically, the PDI ligands are produced through condensation of an appropriate amine or aniline with 2,6-diacetylpyridine and its derivatives. If desired, the PDI ligands can be further modified by known aromatic substitution chemistry.

[0054] In the process of the invention, the catalysts can be unsupported or immobilized on a support material, for example, carbon, silica, alumina, MgCl ₂ or zirconia, or on a polymer or prepolymer, for example polyethylene, polypropylene, polystyrene, poly(aminostyrene), or sulfonated polystyrene. The metal complexes can also be supported on dendrimers. [0055] In some embodiments, for the purposes of attaching the metal complexes of the invention to a support, it is desirable that at least one of R ¹ to R ⁹ of the metal complexes, preferably R ⁶ , has a functional group that is effective to covalently bond to the support. Exemplary functional groups include but are not limited to SH, COOH, NH ₂ or OH groups.

[0056] In one embodiment, silica supported catalyst may be prepared via Ring-Opening Metathesis Polymerization (ROMP) technology as discussed in the literature, for example Macromol. Chem. Phys. 2001, 202, No. 5, pages 645-653; Journal of Chromatography A, 1025 (2003) 65-71.

[0057] One way to immobilize catalysts on the surface of dendrimers is by the reaction of Si-Cl bonded parent dendrimers and functionalized PDI in the presence of a base is as illustrated by Kim et al. in Journal of Organometallic Chemistry 673 (2003) 77-83.

[0058] The unsaturated compound containing at least one unsaturated functional group utilized in the process of the invention can be a compound having one, two, three, or more unsaturations. Examples of such unsaturated compounds include an olefin, a cycloalkene, unsaturated polyethers such as an alkyl-capped allyl polyether, a vinyl-functional alkyl-capped allyl or methallyl polyether, an alkyl-capped terminally unsaturated amine, an alkyne, terminally unsaturated acrylate or methacrylate, unsaturated aryl ether, vinyl-functionalized polymer or oligomer, vinyl-functionalized silane, vinyl-functionalized silicone, unsaturated fatty acids, unsaturated esters, and combinations thereof.

[0059] Unsaturated polyethers suitable for the dehydrogenative silylation reaction preferably are polyoxyalkylenes having the general formula:

R ¹⁰ (OCH ₂ CH ₂ ) _z (OCH ₂ CHR ⁿ ) _w -OR ¹² (Formula III) or

R ¹² 0(CHR ⁿ CH ₂ 0) _w (CH ₂ CH ₂ 0) _z -CR ¹³ ₂ -C≡C-CR ¹³ ₂ - (OCH ₂ CH ₂ ) _z (OCH ₂ CHR ⁿ ) _w R ¹² (Formula IV) or

H ₂ C=CR ¹¹ CH ₂ 0(CH ₂ CH ₂ 0) _z (CH ₂ CHR ¹¹ ) _w CH ₂ CR ¹³ =CH ₂ (Formula V) wherein R ¹⁰ denotes an unsaturated organic group containing from 2 to 10 carbon atoms such as allyl, methylallyl , propargyl or 3-pentynyl. When the unsaturation is olefmic, it is desirably terminal to facilitate smooth dehydrogenative silylation and/or hydrosilylation. However, when the unsaturation is a triple bond, it may be internal. R 12 is hydrogen, vinyl, or a polyether capping group of from 1 to 8 carbon atoms such as the alkyl groups: CH ₃ , n-C ₄ H , t-C ₄ ¾ or i-C ₈ Hi ₇ , the acyl groups such as CH ₃ COO, t-C ₄ Hc,COO, the beta-ketoester group such as CH ₃ C(0)CH ₂ C(0)0, 11 13

or a trialkylsilyl group. R and R are monovalent hydrocarbon groups such as the CI - C20 alkyl groups, for example, methyl, ethyl, isopropyl, 2-ethylhexyl, dodecyl and stearyl, or the aryl groups, for example, phenyl and naphthyl, or the alkaryl or aralkyl groups, for example, benzyl, phenylethyl and nonylphenyl, or the cycloalkyl groups, for example, cyclohexyl and cyclooctyl. R 13 may also

11 13

be hydrogen. Methyl is the most preferred R and R groups. Each occurrence of z is 0 to 100 inclusive and each occurrence of w is 0 to 100 inclusive. Preferred values of z and w are 1 to 50 inclusive.

[0060] Specific examples of preferred unsaturated compounds useful in the process of the present invention include Ν,Ν-dimethylallyl amine, allyloxy-substituted polyethers, propylene, 1-butene, 1- hexene, styrene,, vinylnorbornane, 5-vinyl-norbornene, long-chain, linear alpha olefins such as 1- octadecene, internal olefins such as cyclopentene, cyclohexene, norbornene, and 3-hexene, branched olefins such as isobutylene and 3-methyl-l-octene, unsaturated polyolefms, e.g., polybutadiene, polyisoprene and EPDM, unsaturated acids or esters such as oleic acid, linoleic acid and methyl oleate, a vinyl siloxane of the Formula VI and combinations thereof, wherein Formula VI is

(VI)

wherein each occurrence of R ¹⁴ is independently a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, vinyl, aryl, or a substituted aryl, and n is greater than or equal to zero. In one embodiment, n is 0-500, 1- 250, 50-150, etc. Here, as elsewhere in the specification and claims, numerical values may be combined to form new and non-disclosed ranges. As defined herein, "internal olefin" means an olefin group not located at a chain or branch terminus, such as 3-hexene.

[0061] The silyl hydride employed in the reaction is not particularly limited. It can be any compound selected from the group consisting of R _a SiH ₄ _ _a, (RO) _a SiH ₄ _ _a , Q _u T _v T _p ^H D _w D ^H _x M ^H _y M _z , and combinations thereof. The silyl hydride can contain linear, branched or cyclic structures, or combinations thereof. As used herein, each occurrence of R is independently CI -CI 8 alkyl, Cl-

C18 substituted alkyl, wherein R optionally contains at least one heteroatom, each occurrence of a independently has a value from 0 to 3, each of p, u, v, y and z independently has a value from 0 to

20, w and x are from 0 to 500, provided that p + x + y equals 1 to 500 and the valences of the all the elements in the silyl hydride are satisfied. Preferably, p, u, v, y, and z are from 0 to 10, w and x are from 0 to 100, wherein p+ x + y equals 1 to 100. [0062] As used herein , an "M" group represents a monofunctional group of formula R' ₃ SiOi _/2 , a "D" group represents a difunctional group of formula R' ₂ Si0 _2/2 , a "T" group represents a trifunctional group of formula R'Si03/ ₂ , and a "Q" group represents a tetrafunctional group of formula S1O4/2, an "M ^H " group represents HR' ₂ SiOi/ ₂ , a "T ^H " represents HS1O3/2, and a "D ^H " group represents R'HSi0 _2/2 . Each occurrence of R' is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, wherein R' optionally contains at least one heteroatom.

[0063] Examples of silyl hydrides containing at least one silylhydride functional group include RaSiH ₄ _a, (RO)aSiH ₄ _ _a , HSiR _a (OR) ₃ -a, R ₃ Si(CH ₂ ) _f (SiR ₂ 0) _k SiR ₂ H, (RO) ₃ Si(CH ₂ ) _f (SiR ₂ 0) _k SiR ₂ H, Q _u T _v T _p ^H D _w D ^H _x M ^H _y M _z ,, and combinations thereof, wherein Q is Si0 _4/2 , T is R'Si0 ₃ / ₂ , T ^H is HS1O ₃ / ₂ , D is R' ₂ Si02/2 , D ^H is R'HSi0 ₂ / ₂ , M ^H is HR' ₂ SiOi _/2 , M is R' ₃ SiOi/ ₂ , each occurrence of R and R' is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl, or substituted aryl, wherein R and R' optionally contain at least one heteroatom, each occurrence of a independently has a value from 1 to 3 (with the proviso that the silicon remains tetravalent), f has a value of 1 to 8, k has a value of 1 to 11 , g has a value of from 1 to 3, p is from 0 to 20, u is from 0 to 20, v is from 0 to 20, w is from 0 to 1000, x is from 0 to 1000, y is from 0 to 20, and z is from 0 to 20, provided that p+ x + y equals 1 to 3000, and the valences of the all the elements in the silyl hydride are satisfied. In the above formulations, p, u, v, y, and z may also be from 0 to 10, w and x may be from 0 to 100, wherein p + x + y equals 1 to 100.

[0064] The instant invention also provides hydrosilylation with hydridosiloxanes comprising carbosiloxane linkages (for example, Si-CH ₂ -Si-0-SiH, Si-CH ₂ -CH ₂ -Si-0-SiH or Si-arylene-Si-O- SiH). Carbosiloxanes contain both the -Si-(hydrocarbylene)-Si- and -Si-O-Si- functionalities, where hydrocarbylene represents a substituted or unsubstituted, divalent alkylene, cycloalkylene or arylene group. The synthesis of carbosiloxanes is disclosed in U.S. Patent No. 7,259,220; U.S. Patent No. 7,326,761 and U.S. Patent No. 7,507,775 all of which are incorporated herein in their entirety by reference. An exemplary formula for hydridosiloxanes with carbosiloxane linkages is R ₃ Si(CH ₂ R) _x SiOSiR ₂ (OSiR ₂ ) _y OSiR ₂ H, wherein each occurrence of R is independently a monovalent alkyl, cycloalkyl or aryl group. In one embodiment, R is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl, or substituted aryl. In one embodiment, R is chosen from methyl, ethyl, cyclohexyl or phenyl. Additionally, R in the hydridosiloxane with carbosiloxane linkages, independently may also be H. The subscript x has a value of 1-8, y has a value from zero to 10 and is preferably zero to 4. A specific example of a hydridocarbosiloxane is (CH ₃ ) ₃ SiCH ₂ CH ₂ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ H.

[0065] In one embodiment, the silyl hydride has one of the following structures: R ¹⁵ _a (R ¹⁶ 0) _b SiH (Formula VII)

VIII),

(Formula X) wherein each occurrence of R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ is independently a CI -CI 8 alkyl, CI-

20

C18 substituted alkyl, aryl, or substituted aryl, R is hydrogen, a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl, or substituted aryl, x and w are independently greater than or equal to 0 (x is at least equal to 1 for Formula VIII)), and a and b are integers from 0 to 3 provided that a + b = 3.

[0066] Effective catalyst usage for dehydrogenative silylation ranges from 0.01 mole percent to 10 mole percent based on the molar quantity of the alkene to be reacted. In one embodiment, the catalyst level is 0.01 mole percent to 10 mole percent, 0.05 mole percent to 7.5 mole percent, 0.1 to 5 mole percent, 0.5 to 2.5 mole percent, even 1 to 2 mole percent. Reaction may be run at temperatures from about 0°C up to 300°C, depending on the thermal stability of the alkene, silyl hydride and the specific pyridine diimine complex. Temperatures in the range, 20 - 100°C, have been found to effective for most reactions. Heating of reaction mixtures can be done using conventional methods as well as with microwave devices.

[0067] The dehydrogenative silylation and/or hydrosilylation reactions of this invention can be run at subatmospheric and suprastmospheric pressures. Typically, pressures from about 1 atmosphere (0.1 MPa) to about 200 atmospheres (20 MPa), preferably to about 50 atmospheres (5.0 MPa), are suitable. Higher pressures are effective with volatile and/or less reactive alkenes which require confinement to enable high conversions. [0068] A variety of reactors can be used in the process of this invention. Selection is determined by factors such as the volatility of the reagents and products. Continuously stirred batch reactors are conveniently used when the reagents are liquid at ambient and reaction temperature. These reactors can also be operated with a continuous input of reagents and continuous withdrawal of dehydrogenatively silylated reaction product.

[0069] With gaseous or volatile olefins and silanes, fluidized-bed reactors, fixed-bed reactors and autoclave reactors can be more appropriate. Alternatively, the cobalt pyridinediimine catalyst can be placed in an autoclave reactor, or supported in a catalyst basket therein, and the reagents charged and maintained at the selected temperature and pressure to effect the dehydrogenative silylation and/or hydrosilylation.

[0070] The catalysts of the invention are useful for catalyzing dehydrogenative silylation and/or hydrosilylation reactions. An example is shown in the reaction scheme below.

[0071] The reactions are typically facile at ambient temperatures and pressures, but can also be run at lower or higher temperatures (0 to 300°C) or pressures (ambient to 205 atmospheres, (0.1 - 20.5 MPa)). A range of unsaturated compounds can be used in this reaction, such as N,N-dimethylallyl amine, allyloxy-substituted polyethers, cyclohexene, and linear alpha olefins (i.e., 1-butene, 1- octene, 1-dodecene, etc.).

[0072] Because the double bond of an alkene is preserved during the dehydrogenative silylation reaction employing these cobalt catalysts, a singly-unsaturated olefin may be used to crosslink silyl- hydride containing polymers. Alternatively, an unsaturated siloxane polymer may be used in a hydrosilylation reaction to produce a cross-linked product. A variety of new materials can be produced by this method by varying the hydride polymer and length of the olefin used for the crosslinking. Accordingly, the catalysts used in the process of the invention have utility in the preparation of useful silicone products, including, but not limited to, coatings, for example release coatings, room temperature vulcanizates, sealants, adhesives, products for agricultural and personal care applications, and silicone surfactants for stabilizing polyurethane foams.

[0073] Furthermore, the dehydrogenative silylation and/or hydrosilylation may be carried out on any of a number of unsaturated polyolefms, such as polybutadiene, polyisoprene or EPDM-type copolymers, to either functionalize these commercially important polymers with silyl groups or crosslink them via the use of hydrosiloxanes containing multiple SiH groups at lower temperatures than conventionally used. This offers the potential to extend the application of these already valuable materials in newer commercially useful areas.

[0074] In one embodiment, the catalysts are useful for dehydrogenative silylation and/or hydrosilylation of a composition containing a silyl hydride and a compound having at least one unsaturated group. The process includes contacting the composition with a metal complex of the catalyst, either supported or unsupported, to cause the silyl hydride to react with the compound having at least one unsaturated group to produce a dehydrogenative silylation and/or hydrosilylation product, which may contain the metal complex catalyst. The dehydrogenative silylation and/or hydrosilylation reaction can be conducted optionally in the presence of a solvent. If desired, when the dehydrogenative silylation and/or hydrosilylation reaction is completed, the metal complex can be removed from the reaction product by magnetic separation and/or filtration. These reactions may be performed neat, or diluted in an appropriate solvent. Typical solvents include benzene, toluene, diethyl ether, etc. It is preferred that the reaction is performed under an inert atmosphere. The catalyst can be generated in-situ by reduction using an appropriate reducing agent.

[0075] The manner or order in which the respective components for carrying out the process are added to one another is not particularly limited and can be chosen as desired. In one embodiment, the silylhydride can be added to a mixture containing the metal complex and the unsaturated olefin. In another embodiment, the unsaturated olefin can be added to a mixture containing the metal complex and the silylhydride. In still another embodiment, a mixture of silylhydride and unsaturated olefin can be added to a mixture of metal complex, silylhydride and unsaturated olefin. It will be appreciated that the first mixtures in the above embodiments may be heated or preliminarily reacted prior to addition of the remaining components.

[0076] The catalyst complexes of the invention are efficient and selective in catalyzing dehydrogenative silylation and/or hydrosilylation reactions. For example, when the catalyst complexes of the invention are employed in the dehydrogenative silylation and/or hydrosilylation of an alkyl-capped allyl polyether or a compound containing an unsaturated group, the reaction products are essentially free of unreacted alkyl-capped allyl polyether and its isomerization products. In one embodiment, the reaction products do not contain the unreacted alkyl-capped allyl polyether and its isomerization products. Further, when the compound containing an unsaturated group is an unsaturated amine compound, the dehydrogenatively silylated and/or hydrosilylated product is essentially free of internal addition products and isomerization products of the unsaturated amine compound. As used herein, "essentially free" is meant no more than 10 wt%, preferably 5 wt% based on the total weight of the hydrosilylation product. "Essentially free of internal addition products" is meant that silicon is added to the terminal carbon. [0077] The following examples are intended to illustrate, but in no way limit the scope of the present invention. All parts and percentages are by weight and all temperatures are in degrees Celsius unless explicitly stated otherwise. All the publications and the US patents referred to in the application are hereby incorporated by reference in their entireties.

EXAMPLES

General Considerations

[0078] All air- and moisture-sensitive manipulations were carried out using standard vacuum line, Schlenk (Argon), and cannula techniques or in an MBraun inert atmosphere dry box containing an atmosphere of purified nitrogen. Solvents for air- and moisture-sensitive manipulations were initially dried and deoxygenated using literature procedures described in Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics 1996, 15, 1518. SilForce ^® SL6100 (M ^vi Di ₂₀ M ^vi ), SilForce ^® SL6020 (MDi ₅ D ^H ₃₀ M) were acquired from Momentive Performance Materials and dried under high vacuum for 12 hours before use.

[0079] All silanes and alkene substrates are dried over CaH ₂ or LiAlH ₄ , then distilled under vacuum and stored under N ₂ . 1H NMR spectra were recorded on Bruker AVANCE 300, Varian Inova 400 and Bruker AVANCE 500 spectrometers operating at 300.13, 399.78, and 500.62 MHz, respectively. 13 C NMR spectra were either recorded on a Bruker 500 spectrometer operating at 125.853 MHz. All 1H and ¹³ C NMR chemical shifts are reported relative to SiMe ₄ using the 1H

13

(residual) and C chemical shifts of the solvent as a secondary standard. GC analyses were performed using a Shimadzu GC-2010 gas chromatograph equipped with a Shimadzu AOC-20s autosampler and a Shimadzu SHRXI-5MS capillary column (15m x 250μιη). The instrument was set to an injection volume of 1 μί, an inlet split ratio of 20: 1, and inlet and detector temperatures of 250°C and 275°C, respectively. UHP-grade helium was used as carrier gas with a flow rate of 1.82 mL/min. The temperature program used for all the analyses is as follows: 60 °C, 1 min; 15 °C/min to 250 °C, 2 min.

[0080] Catalyst loadings in the following text are reported in mol% of the cobalt complex (molc _o complex / mololefin 100).

Attempted synthesis of ^Me APDICoMe

[0081] This procedure is based upon that used for the synthesis of ^Me APDICoNs {vide supra) In a nitrogen-filled drybox, a scintillation vial was charged with 0.078 g (0.244 mmol) of ^Me APDICoCl ₂ and approximately 8 mL of THF. The suspension was chilled at -35 °C for 20 minutes. To this suspension was then added dropwise a diethyl ether solution of methyllithium (1.60 M in diethyl ether, 0.306 mL), during which time a solution color change to black with concomitant formation of dark precipitate was observed. The reaction mixture was stirred at room temperature for 3 hours, after which the volatiles were removed in vacuo. The residue contained a complex mixture of unidentified cobalt-containing products. Notably no evidence for the formation

Example 1. Synthesis of ^vle APDICoNs

[0082] In a nitrogen-filled drybox, a scintillation vial was charged with 0.350 g (1.097 mmol) of ^Me APDICoCl ₂ and approximately 14 mL of THF. The suspension was chilled at -35 °C for 20 minutes. To this suspension was then added dropwise a THF solution of (trimethylsilyl)methyllithium (0.207 g in 3 mL THF), during which time a solution color change to purple was observed. The reaction mixture was stirred at room temperature overnight, after which the volatiles were removed in vacuo. The residue was extracted with diethyl ether, filtered through Celite, and concentrated. Layering the supernatant with pentane and recrystallization at -35 °C yielded 0.155 g (42%) of a purple solid identified as ^Me APDICoNs. 1H NMR (benzene- ₆ , 23 °C): δ = 9.83 (t, 8 Hz, 1H), 7.21 (d, 8 Hz, 2H), 3.98 (s, 6H), 1.22 (s, 2H), -0.11 (s, 9H), -0.57 (s, 6H). ¹³ C

Example 2. Synthesis of ^APDICoNs

[0083] In a nitrogen-filled drybox, a scintillation vial was charged with 0.134 g (0.386 mmol) of ^Et APDICoCl ₂ and approximately 10 mL of THF. The suspension was chilled at -35 °C for 20 minutes. To this suspension was then added dropwise a THF solution of (trimethylsilyl)methyllithium (0.073 g in 1 mL THF), during which time a solution color change to purple was observed. The reaction mixture was stirred at room temperature overnight, after which the volatiles were removed in vacuo. The residue was extracted with toluene, filtered through Celite, and concentrated. Layering the supernatant with pentane and recrystallization at -35 °C yielded 0.093 g (66.3%) of a purple solid identified as ^Et APDICoNs. 1H NMR (benzene- e, 23 °C): δ = 9.80 (t, 8 Hz, 1H), 7.28 (d, 8 Hz, 2H), 5.21 (q, 7 Hz, 4H), 1.70 (t, 7 Hz, 6H), 1.17 (s, 2H), -0.13 (s, 9H), -0.37 (s, 6H). ¹³ C NMR (benzene- ₆ , 23 °C): δ = 162.77, 152.73, 122.55, 114.03, 53.59,

Example 3. Synthesis of ^Ly APDICoNs

[0084] In a nitrogen-filled drybox, a scintillation vial was charged with 0.280 g (0.667 mmol) of ^Cy APDICoCl (Bowman, A. C; Milsmann, C; Bill, E.; Lobkovsky, E.; Weyhermuller, T.; Wieghardt, K.; Chirik, P. J. Inorg. Chem. 2010, 49, 6110-6123) and approximately 14 mL of diethyl ether. The suspension was chilled at -35 °C for 20 minutes. To this suspension was then added dropwise a diethyl ether solution of (trimethylsilyl)methyllithium (0.066 g in 3 mL diethylether), during which time a solution color change from orange to purple was observed. The reaction mixture was stirred at room temperature for 1 hour, after which time the mixture was filtered through Celite, and concentrated. Layering the supernatant with pentane and recrystallization at -35 °C yielded 0.250 g (79%) of a purple solid identified as ^Cy APDICoNs. 1H NMR (benzene- e, 23 °C): δ = 9.68 (t, 8 Hz, 1H), 7.43 (d, 8 Hz, 2H), 6.93 (br, 2H), 4.27 (m, 2H), 3.15-1.18 (m, 20H), -0.01 (s, 6H), -0.45 (s, 9H). ¹³ C NMR (benzene- ₆ , 23 °C): δ = 158.84, 144.50,

Examples 4-6. General procedure for the silylation of 1-octene with different silanes using ^APDICoNs.

[0085] In a nitrogen-filled drybox, a scintillation vial was charged with 0.100 g (0.891 mmol) of 1- octene and 0.002 g (0.004 mmol) ^Cy APDICoNs (0.5 mol %), 0.891 mmol of silane (0.146 g (EtO) ₃ SiH, 0.198 g of MD ^H M or 0.104 g of Et ₃ SiH) was then added to the mixture and the reaction was stirred at room temperature for desired amount of time. The product mixture was quenched by exposure to air. The product mixture was filtered through a plug of silica gel (Fluka® high-purity grade, pore size 60 , 230-400 mesh particle size, 40-63 μιη particle size, for flash chromatography) and eluted with hexane. The crude product mixture was analyzed by GC. Volatiles were then 1 13 removed from the crude mixture product and the resulting mixture was analyzed by H and C NMR spectroscopy.

octene isomers > 95%

neat, 23 °C, 24 h

Examples 7-9. General procedure for the silylation of 1 -octene with different silanes using ^Et APDICoNs.

[0086] In a nitrogen-filled drybox, a scintillation vial was charged with 0.100 g (0.891 mmol) of 1- octene and 0.002 g (0.004 mmol) ^Et APDICoNs (0.5 mol %), 0.891 mmol of silane (0.146 g (EtO) ₃ SiH, 0.198 g of MD ^H M or 0.104 g of Et ₃ SiH) was then added to the mixture and the reaction was stirred at room temperature for desired amount of time. The product mixture was quenched by exposure to air. The product mixture was filtered through silica gel and eluted with hexane. The product mixture was directly injected to GC. The resulting solution was dried under vacuum and the

1 13

remaining residue was analyzed by H and C NMR spectroscopy. The yields are based on conversion of 1 -octene.

neat, 23 °C, 12 h

Examples 10-12. General procedure for the silylation of 1-octene with different silanes using ^Me APDICoNs.

[0087] In a nitrogen-filled drybox, a scintillation vial was charged with 0.100 g (0.891 mmol) of 1- octene and approximately 0.001 g (0.004 mmol) ^Me APDICoNs (0.5 mol %), 0.891 mmol of silane (0.146 g (EtO) ₃ SiH, 0.198 g of MD ^H M or 0.104 g of Et ₃ SiH) was then added to the mixture and the reaction was stirred at room temperature for desired amount of time. The product mixture was quenched by exposure to air. The product mixture was filtered through silica gel and eluted with hexane. The product mixture was directly injected to GC. The resulting solution was dried under

1 13

vacuum and the remaining residue was analyzed by H and C NMR spectroscopy. The yields are based on conversion of 1-octene.

neat, 23 °C, 1 h

Example 13. Silylation of 1-octene with l-(2-trimethylsilylethyl)-l,l,3,3-tetramethyldisiloxane using ^Me APDICoNs

[0088] In a nitrogen-filled drybox, a scintillation vial was charged with 0.100 g (0.891 mmol) of 1- octene and approximately 0.001 g (0.004 mmol) ^Me APDICoNs (0.5 mol %). l-(2- trimethylsilylethyl)-l,l,3,3-tetramethyldisiloxane (0.209 g, 0.891 mmol) was then added to the mixture and the reaction was stirred at room temperature for 1 hour, after which the mixture was quenched by exposure to air. The product mixture was filtered through silica gel and eluted with hexane. The crude product mixture was analyzed by GC. Volatiles were then removed from the

1 13

crude mixture product and the resulting mixture was analyzed by H and C NMR spectroscopy.

neat, 23 °C, 1 h

Example 14. Silylation of 1-octene with 2-(trimethylsilyl)ethyldimethylsilane using

M ^e APDICoNs

[0089] In a nitrogen-filled drybox, a scintillation vial was charged with 0.100 g (0.891 mmol) of 1- octene and approximately 0.001 g (0.004 mmol) ^Me APDICoNs (0.5 mol %). 2-(trimethylsilyl)ethyldimethylsilane (0.143 g, 0.891 mmol) was then added to the mixture and the reaction was stirred at room temperature for 1 hour, after which the mixture was quenched by exposure to air. The product mixture was filtered through silica gel and eluted with hexane. The crude product mixture was analyzed by GC. Volatiles were then removed from the crude product

1 13

mixture and the residue was analyzed by H and C NMR spectroscopy.

neat, 23 °C, 1 h

Example 15. Catalytic hydrosilylation of 1-octene with (EtO) ₃ SiH at low ^vle APDICoNs loading

[0090] In a nitrogen- filled drybox, a scintillation vial was charged with 0.400 g (3.56 mmol) of 1- octene and 100 μΐ _^ οΐ a 16 mM toluene solution of ^Me APDICoNs. Then to the mixture was added 0.586 g of (EtO) ₃ SiH dropwise over a period of 20 seconds and the resulting reaction mixture was stirred at room temperature for 80 minutes. The product mixture was quenched by exposure to air. The product mixture was filtered through silica gel and eluted with hexane. The product mixture was analyzed by GC.

Example 16. Catalytic hydrosilylation of 1-octene with (EtO) ₃ SiH at elevated temperature using ^Me APDICoNs

[0091] In a nitrogen- filled drybox, a scintillation vial was charged with 0.400 g (3.56 mmol) of 1- octene and 200 μΐ _^ of a 4 mM toluene solution of ^Me APDICoNs. Then to the mixture was added 0.586 g of (EtO) ₃ SiH dropwise over a period of 20 seconds and the resulting reaction mixture was stirred at 60 °C for 3 hours. The product mixture was quenched by exposure to air. The product mixture was filtered through silica gel and eluted with hexane. The product mixture was analyzed by GC.

Example 17. Cross-linking using Momentive SL6100 and SL6020 Dl using ^vle APDICoNs

[0092] In a nitrogen- filled drybox, a scintillation vial was charged with 3.000 g of mixture of M ^vi Di2 ₀ M ^vi (SL6100) and MDi ₅ D ^H ₃₀ M (SL6020) (in 1 :2 molar ratio). Then to the mixture was added 20 of a 4 mM toluene solution of ^Me APDICoNs (10 ppm Co). The reaction mixture was then stirred at room temperature. Complete gelation was achieved in 1 hour. When the reaction was performed at 80 °C, complete gelation occurred within 1 minute.

Example 18. Silylation of 1-octene with Momentive SL6020 Dl using ^Me APDICoNs

[0093] In a nitrogen-filled drybox, a scintillation vial was charged with 0.100 g (0.891 mmol) of 1- octene, 0.500 g benzene and approximately 0.001 g (0.004 mmol) ^Me APDICoNs, MDi ₅ D ^H ₃₀ M (0.091 g) was then added and the reaction mixture was stirred at room temperature for 1 hour. The product mixture was quenched by exposure to air. The product mixture was filtered through silica gel and eluted with hexane. The product mixture was analyzed by 1H NMR spectroscopy. The 1H NMR (benzene-^) spectrum of the product mixture revealed vinyl proton signals at 5.5-6.0 ppm, characteristic of dehydrogenative silylation.

benzene, 23 °C

Example 19. Silylation of Momentive SL6100 with (EtO) ₃ SiH using ^vle APDICoNs

[0094] In a nitrogen-filled drybox, a scintillation vial was charged with 1.000 g of M ^vl Di2oM ^vl (SL6100), 0.500 g benzene and approximately 0.001 g (0.004 mmol) ^Me APDICoNs, MD ^H M (0.200 g, 0.891 mmol) was then added and the reaction mixture was stirred at room temperature for 1 hour.

The product mixture was quenched by exposure to air. The product mixture was filtered through silica gel and eluted with hexane. The product mixture was analyzed by H NMR spectroscopy. The 1H NMR (benzene-^) spectrum of the product mixture contained no vinyl proton signals, signaling hydrosilylation products. The products were identified as a mixture of anti-Markovnikov and Markovnikov hydrosilylation by their characteristic proton signals (a multiplet at 0.75 ppm for Anti-Markovnikov product; a doublet at 1.3 ppm for Markovnikov product)

Example 20. Silylation of allyl(poly)ether (Y10227) with (EtO) ₃ SiH using ^vle APDICoNs

[0095] In a nitrogen-filled drybox, a scintillation vial was charged with 0.279 g of Y10227 (6.88% vinyl content) and approximately 0.001 g of ^Me APDICoNs (0.004 mmol, 1 mol %), (EtO) ₃ SiH (0.075 g, 0.457 mmol) was then added and the reaction mixture was stirred at 50 °C for 1 hour. The product mixture was quenched by exposure to air. The product mixture was filtered through silica gel and eluted with hexane. The product mixture was analyzed by 1H NMR spectroscopy. The 1H NMR (benzene-^) spectrum contained no olefmic peaks, and characteristic alpha-Si methylene CH ₂ signals were observed at 0.71 ppm indicating formation of Anti-Markovnikov hydrosilylation product.

neat, 50°C, 1 hr

Examples 21-34. General procedure for the silylation of vinylsilane with different silanes using ^Me APDICoNs, ^Et APDICoNs or ^Cy APDICoNs

[0096] In a nitrogen-filled drybox, a scintillation vial was charged with 0.089 g (0.891 mmol) of trimethyl(vinyl)silane and 0.004 mmol (0.5 mol %) of cobalt catalyst (0.002 g of ^Cy APDICoNs, 0.002 g of ^APDICoNs or 0.001 g of ^Me APDICoNs), 0.891 mmol of silane (0.146 g of (EtO) ₃ SiH or 0.198 g of MD ^H M) was then added to the mixture and the reaction was stirred at room temperature for desired amount of time. The product mixture was quenched by exposure to air. The product mixture was filtered through silica gel and eluted with hexane. The resulting solution was

1 13

dried under vacuum and the remaining residue was analyzed by H and C NMR spectroscopy.

[Co] [Si]-H A B C

^Me APDICoNs (EtO) ₃ SiH 0 57 43

MD ^H M 0 76 24

^Et APDICoNs (EtO) ₃ SiH 0 33 67

MD ^H M 1 60 39

CyAPDICoNs (EtO) ₃ SiH 0 3 97

MD ^H M 8 84 8 [Si]

A B c D

[Co] t (95% conv.) [Si] [Si]'-H A B c D

^Me APDICoNs 1 h SiMe(OSiMe ₃ ) ₂ (EtO) ₃ SiH 38.5 61.5

1 h SiMe(OSiMe ₃ ) ₂ MD ^H M 23 - 77 - 1 h Si(OEt) ₃ (EtO) ₃ SiH 8.5 91.5

1 h Si(OEt) ₃ MD ^H M 40 60

cyAPDICoNs 1 h SiMe(OSiMe ₃ ) ₂ (EtO) ₃ SiH 72 27 1

12 h SiMe(OSiMe ₃ ) ₂ MD ^H M 2.5 16 30 51.5

1 h Si(OEt) ₃ (EtO) ₃ SiH 43 57

12 h Si(OEt) ₃ MD ^H M 14 85 1

Representative example (21) of hydrosilylation of trimethyl(vinyl)silane with (EtO) ₃ SiH using ^Me APDICoNs

[0097] According to the general procedure described above, the product is a mixture of triethoxy(2- (trimethylsilyl)ethyl)silane and triethoxy(l-(trimethylsilyl)ethyl)silane in 57:43 ratio.

[0098] Characterization for triethoxy(2-(trimethylsilyl)ethyl)silane: 1H NMR (benzene-d ₆ , 23 °C): δ = 3.81 (q, 7 Hz, 6H), 1.17 (t, 7 Hz, 9H), 0.76-0.64 (m, 4H), -0.02 (s, 9H); ¹³ C NMR (benzene- e, 23 °C): δ = 58.56, 18.64, 8.28, 3.39, -2.15

[0099] Characterization for triethoxy(l-(trimethylsilyl)ethyl)silane: 1H NMR (benzene-d ₆ , 23 °C): δ = 3.77 (q, 7 Hz, 6H), 1.15 (t, 7 Hz, 9H), 0.20 (s, 9H), 0.06 (q, 7 Hz, 1H); ¹³ C NMR (benzene- ₆ , 23 °C): δ = 58.57, 18.69, 8.75, 3.82, -1.10

neat, 23 °C, 1 h

Representative example (26) of hydrosilylation of trimethyl(vinyl)silane with MD ^H M using ^APDICoNs

[00100] According to the general procedure described above, the product is a mixture of

1 ,1 , 1 ,3,5,5,5-heptamethyl-3-(2-(trimethylsilyl)ethyl)trisiloxane, (E)-l , 1 ,1 ,3,5,5,5-heptamethyl-3-(2- (trimethylsilyl)vinyl)trisiloxane and 1 , 1 ,1 ,3 ,5 ,5 ,5 -heptamethyl-3 -( 1 -(trimethylsilyl)ethyl)trisiloxane in 84:8:8 ratio.

[00101] Characterization of l ,l , l ,3,5,5,5-heptamethyl-3-(2-(trimethylsilyl)ethyl)trisiloxane:

1H NMR (benzene- ₆ , 23 °C): δ = 0.56-0.42 (m, 4H), 0.30-0.10 (m, br, 30H); ¹³ C NMR (benzene- ₆ , 2 °C): δ = 10.1 -0.76, -2.00.

Example 35. General procedure for Co-catalyzed hydrosilation of alkynes

[00102] To a scintillation vial equipped with stir bar under nitrogen was added ^Me APDICoNs

(0.003 g) followed by triethoxysilane (0.149 g) and 1-octyne (100 mg, 1.00 equiv.). The vial was sealed with a cap and heated to 80 °C in an oil bath for 3 hours. After cooling to ambient temperature, the resulting dark reaction mixture was exposed to air to destroy remaining catalyst. The volatiles were removed with a stream of air and the resulting residue was diluted with a solution of 5% ethyl ether in pentane and passed through a small column of silica gel, eluting with additional 5% ether in pentane solution (5 mL). The resulting clear, colorless eluent was concentrated to give the product mixture as a clear, colorless oil (237 mg, 95%). Analysis of the

1 13

product by both H and C NMR established the product ratio shown below. All spectra are in accordance with the literature values ( Bo, G. D.; Berthon-Gelloz, G.; Tinant, B.; Marko, I. E. OrganometaUics 2006, 25,

neat, 80 °C, 3 h

[(3)]

Example 36A-36C: Silylation of propylene with different silanes using ( ^Mes PDI)CoCH ₃ .

[00103] This reaction was carried out in a manner similar to the silylation of 1-butene using

0.1 1 mmol of silane (0.025 g of MD ^H M, 0.018 g of (EtO) ₃ SiH or 0.015 g of (OEt) ₂ CH ₃ SiH) 0.001 g (0.002 mmol) of ( ^Mes PDI)CoCH ₃ and 5.6 mmol (50 equiv) of propylene. The non-volatiles were analyzed by NMR spectroscopy.

Table 12. Product Distribution for the Silylation of Propylene.

Characterization of Products of Example 36A:

[00104] 3-bis(trimethylsiloxy)methylsilyl-l-propene. 1H NMR (CDC1 ₃ ): δ = 0.03 (s, 3H,

(OTMS) ₂ SiCH ₅ ), 0.09 (s, 18H, OSi(CH ₅ ) ₃ ), 1.49 (d, J = 8.1 Hz, 2H, SiCH ₂ CH=CH), 4.86 (d, J = 6.3 Hz, 1H, CH ₂ CH=C(H)H), 4.88 (d, J = 15 Hz, 1H, CH ₂ CH=C(H)H), 5.77 (m, 1H, CH ₂ CH=CH ₂ ). ¹³ C {1H} NMR (CDC1 ₃ ): δ = -0.77 ((OTMS) ₂ SiCH ₃ ), 1.97 (OSi(CH ₃ ) ₃ ), 25.82 (SiCH ₂ CH=CH), 1 13.72 (CH ₂ CH=CH ₂ ), 134.28 (CH ₂ CH=CH ₂ ).

[00105] l-bis(trimethylsiloxy)methylsilylpropane. 1H NMR (CDC1 ₃ ): δ = 0.00 (s, 3H,

(OTMS) ₂ SiCH ₅ ), 0.09 (s, 18H, OSi(CH ₅ ) ₃ ), 0.46 (m, 2H, SiCH ₂ CH ₂ CH ₃ ), 0.95 (t, 3H, SiCH ₂ CH ₂ CH ₅ ), 1.36 (m, 2H, SiCH ₂ CH ₂ CH ₃ ). ¹³ C {1H} NMR (CDC1 ₃ ): δ = -0.07 ((OTMS) ₂ SiCH ₃ ), 1.97 (OSi(CH ₃ ) ₃ ), 16.75 (SiCH ₂ CH ₂ CH ₃ ), 18.05 (SiCH ₂ CH ₂ CH ₃ ), 20.37 (SiCH ₂ CH ₂ CH ₃ ). Characterization of Products of Example 36B:

[00106] 3-triethoxysilyl-l-propene. 1H NMR (CDC1 ₃ ): δ = 1.22 (t, 9H, OCH ₂ C¾), 1.67 (d, 2Η, SiCH ₂ CH=CH), 3.84 (q, 6H, OCH ₂ CH ₃ ), 4.90-5.05 (d, 2H, CH ₂ CH=CH ₂ ), 5.81 (m, 1Η, CH ₂ CH=CH ₂ ). ¹³ C {1H} NMR (CDCI ₃ ): δ = 18.36 (OCH ₂ CH ₃ ), 19.34 (SiCH ₂ CH=CH), 58.73 (OCH ₂ CH ₃ ), 1 14.85 (CH ₂ CH=CH ₂ ), 132.80 (CH ₂ CH=CH ₂ ).

[00107] 1-triethoxysilylpropane. 1H NMR (CDC1 ₃ ): δ = 0.63 (m, 2H, SiC¾CH ₂ CH ₃ ), 0.97

(t, 3H, SiCH ₂ CH ₂ C¾), 1.22 (t, 9Η, OCH ₂ C¾), 1.45 (m, 2H, SiCH ₂ CH ₂ CH ₃ ), 3.84 (q, 6H, OCH ₂ CH ₃ ). ¹³ C {1H} NMR (CDCI ₃ ): δ = 10.94 (SiCH ₂ CH ₂ CH ₃ ), 12.92 (SiCH ₂ CH ₂ CH ₃ ), 16.50 (SiCH ₂ CH ₂ CH ₃ ), 18.43 (OCH ₂ CH ₃ ), 58.40 (OCH ₂ CH ₃ ).

Characterization of Products of Example 36C:

[00108] 3-diethoxymethylsilyl-l-propene. 1H NMR (CDC1 ₃ ): δ = 0.1 1 (s, 3H, SiC¾), 1.19 (t, 6Η, OCH ₂ CH ₅ ), 1.63 (d, 2Η, SiCH ₂ CH=CH), 3.76 (q, 4H, OCH ₂ CH ₃ ), 4.88 (d, 1H, CH ₂ CH=C(H)H), 4.93 (d, 1Η, CH ₂ CH=C(H)H), 5.80 (m, 1H, CH ₂ CH=CH ₂ ). ¹³ C {1H} NMR (CDCI3): δ = -5.19 (SiCH ₃ ), 18.44 (OCH ₂ CH ₃ ), 21.92 (SiCH ₂ CH=CH), 58.41 (OCH ₂ CH ₃ ), 1 14.45 (CH ₂ CH=CH ₂ ), 133.36 (CH ₂ CH=CH ₂ ).

[00109] 1-diethoxymethylsilylpropane: 1H NMR (CDC1 ₃ ): δ = 0.08 (s, 3H, SiC¾), 0.59

(m, 2H, SiCH ₂ CH ₂ CH ₃ ), 0.94 (t, 3H, SiCH ₂ CH ₂ CH ₅ ), 1.19 (t, 6Η, OCH ₂ CH ₅ ), 1.38 (m, 2Η, SiCH ₂ CH ₂ CH ₃ ), 3.76 (q, 4H, OCH ₂ CH ₃ ). ¹³ C {1H} NMR (CDC1 ₃ ): δ = -4.76 (SiCH ₃ ), 16.37 (SiCH ₂ CH ₂ CH ₃ ), 16.53 (SiCH ₂ CH ₂ CH ₃ ), 18.07 (SiCH ₂ CH ₂ CH ₃ ), 18.50 (OCH ₂ CH ₃ ), 58.13 (OCH ₂ CH ₃ ).

[00110] While the above description contains many specifics, these specifics should not be construed as limitations on the scope of the invention, but merely as exemplifications of preferred embodiments thereof. Those skilled in the art will envision many other possible variations that are within the scope and spirit of the invention as defined by the claims appended hereto.