THEIR USE IN HYDRO SILYLATION REACTIONS

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application Ser.

No. 61/823,599 filed May 15, 2013, which is incorporated by reference herein in its entirety.

FIELD OF INVENTION

The invention relates generally to transition metal salts, more specifically to iron, nickel, cobalt, manganese, and ruthenium salts, activated with silylhydrides, and their use as efficient hydrosilylation catalysts.

BACKGROUND OF THE INVENTION

Hydrosilylation chemistry, involving the reaction between a silylhydride and an unsaturated organic group, is the basis for synthetic routes to produce commercial silicone products such as silicone surfactants, silicone fluids and silanes as well as many addition cured products including sealants, adhesives, and silicone-based coatings. Conventionally, hydrosilylation reactions have been typically catalyzed by precious metal catalysts, such as platinum or rhodium metal complexes.

Various precious metal complex catalysts are known in the art. For example, U.S.

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 U.S. Patent No. 3, 159,601, Lamoreaux's catalyst as disclosed in U.S. 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).

Although these precious metal compounds and complexes are widely accepted as catalysts for hydrosilylation reactions, they have several distinct disadvantages. One disadvantage is that the precious metal complex catalysts are inefficient in catalyzing certain reactions. For example, in the case of hydros ilylations of allyl polyethers with silicone hydrides using precious metal complex catalysts, use of a large excess of allyl polyether, relative to the amount of silicone hydride, is needed to compensate for the lack of efficiency of the catalyst in order to ensure complete conversion of the silicone hydride to a useful product. When the hydrosilylation reaction is completed, this excess allyl polyether must either be: (A) removed by an additional step, which is not cost-effective, or (B) left in the

{4883589:} 1 product which can result in reduced performance of this product in end-use applications. Additionally, allyl polyether hydrosilylation with conventional precious metal catalysts typically results in a significant amount of undesired side products such as olefin isomers, which in turn can lead to the formation of undesirably odoriferous byproduct compounds.

Further, due to the high price of precious metals, catalysts derived from these metals can constitute a significant proportion of the cost of silicone formulations. Over the last two decades, global demand for precious metals, including platinum, has sharply increased, driving prices several hundred folds higher, thereby precipitating the need for effective, low cost replacement catalysts.

As an alternative to precious metals, certain iron complexes have been disclosed as suitable for use as ketone and/or aldehyde hydrosilylation catalysts. Illustratively, technical journal articles have disclosed that iron salts treated with phosphine or nitrogen compounds catalyze the hydrosilylation reaction of activated double bonds such as aldehydes and ketones at long reaction times. (Beller et al. Organic Letters, 2007, 26, 5429-5432; Beller et al.

Angew. Chem. Int. Ed., 2008, 47, 2497-2501; Nishiyama et al. Tetrahedron Letters, 2008, 49, 110-113.) Nishiyama (Chem. Commun. 2007, 760-762.) reported the poor activity of iron acetate and 2,6-(2,4,6-Me ₃ -C ₆ H2N=CMe)2C5H ₃ N ( ^Mes PDI) in the hydrosilylation of methyl(4- phenyl)phenylketone ( 7% after 20h at 65°C).

Certain iron complexes have also been disclosed as suitable for use as alkene hydrosilylation catalysts. For example, Fe(CO)s has been shown to catalyze hydrosilylation reactions at high temperatures: Nesmeyanov, A.N. et al, Tetrahedron 1962, 17, 61 ; Corey, J.Y et al, J. Chem. Rev. 1999, 99, 175; C. Randolph, M.S. Wrighton, J. Am. Chem. Soc. 1986, 108, 3366). However, undesirable by-products such as unsaturated silyl-olefins, resulting from dehydrogenative silylation, were formed as well.

A five-coordinate Fe(II) complex containing a pyridine di-imine (PDI) ligand with isopropyl substituents at the ortho positions of the aniline rings has been used to hydrosilylate an unsaturated hydrocarbon (1-hexene) with primary and secondary silanes such as PhSiH ₃ or Ph ₂ SiH ₂ (Bart et al, J. Am. Chem. Soc, 2004, 126, 13794;Archer, A.M. et al.

Organometallics 2006, 25, 4269). However, one limitation of these catalysts is that they are only effective with the aforementioned primary and secondary phenyl-substituted silanes, and not with, for example, tertiary or alkyl-substituted silanes such as EtsSiH, or with alkoxy substituted silanes such as (EtO^SiH.

Recently, new and inexpensive Fe, Ni, Co and Mn complexes containing a terdentate nitro ^p en li ^p and have been found to selectively catalyze hydrosilylation reactions, as described in co-pending U.S. Patent Nos. 8,236,915 and 8,415,443. Chirik has reported the formation of the catalytically inactive Fe(PDI) ₂ species. The undesired Fe(PDI) ₂ is formed by treatment of PDIFeBr ₂ with the reductant Na(Hg). The yield of the Fe(PDI) ₂ species increases when the reduction is performed in the presence of excess free PDI. (Chirik et al. Inorg. Chem. 2010, 49, 2782-2792. Chirik et al. Inorg. Chem. 2009, 48, 4190-4200).

One restriction of these new non-precious metal based catalysts, however, is that they are normally extremely sensitive to air and moisture, and thus are unlikely to perform well or consistently if exposed to air or moisture prior to their use. For this reason, these catalysts are typically prepared and stored under hermetically inert conditions such as in a dry box. Since it is impractical to install and use such highly inert-atmosphere equipment widely on an industrial scale, the use of these catalysts in a commercial setting may be economically prohibitive. Accordingly, there is a need in the industry for non-precious metal-based catalysts that do not require manufacturing and storing under inert conditions.

Methods are known in the art to activate catalyst precursors in-situ. The most well- known example is the activation of Ziegler-Natta catalyst by methylaluminoxane (MAO) for the production of polypropylene from propene (Y. V. Kissin Alkene Polymerization

Reactions with Transition Metal Catalysts, Elsevier, 2008, Chapter 4).

Additional examples of catalyst activation are also known. U.S. Patent No. 5,955,555 discloses the activation of certain iron or cobalt PDI dianion complexes by

polymethylaluminoxane (PMAO) for olefin polymerization. U.S. Patent No. 4,729,821 discloses the in-situ activation of Ni-catalysts by applied electrical potentials for the hydrogenolysis of ethane and ethylene. Martinez et al. demonstrated the in-situ activation of a [RuCl ₂ (p-cym)] ₂ complex by phosphine ligands in a C-C bond formation reaction via C-H bond activation of aryl-compounds (J. Am. Chem. Soc, 2009, 131, 7887). Yi et al. described the in-situ formation of cationic ruthenium hydride complexes which catalyze the regioselective intermolecular coupling reaction of arylketones and alkenes involving C-H bond activation (Organometallics, 2009, 28, 426). More recently, Thomas et al. have described the activation of base metal complexes with ethyl magnesium bromide (Adv. Synth. Catal. 2014, 356(2-3), 584-590).

The in-situ activation of non-precious metal-based catalysts for alkene hydrosilylation reactions has been described. (See, U.S. Patent Application Publication 2012/013106A1). However, this activation employs NaBEtsH, which is sensitive to air and incompatible with alkoxysilanes. Alkoxysilanes are known to undergo dangerous disproportionation reactions with stron ^p hydride donors such as alkali borohydrides or alkali hydrides. (Woo, H.; Song, S.; Cho, E.; Jung, L; Bull Korean Chem. Soc. 1996, 17, 123-125. Itoh, M.; Ihoue, K.;

Ishikawa, J.; Iwata, K. J. Organomet. Chem., 2001, 629 1-6.)

There is a continuing need in the hydros ilylation industry for methods of activating non-precious metal catalysts using milder reducing reagents that are also compatible with alkoxysilanes. The present invention provides one solution toward that need.

SUMMARY OF THE INVENTION

In one aspect, the present invention provides a process for the hydrosilylation of an unsaturated compound in the presence of a metal complex via the activation of the metal complex with a silylhydride and a promoter compound.

In one aspect, the present invention provides a process for the hydrosilylation of an unsaturated compound comprising at least one unsaturated group with a silylhydride in the presence of a metal complex of Formula (I), Formula (II), or a combination thereof:

Formula (I);

GXn Formula (II);

wherein the process comprises activating the metal complex with a silylhydride and a promoter compound, and G is Mn, Fe, Ni, Ru, or Co; each occurrence of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , is independently H, Cl-18 alkyl, CI -CI 8 substituted alkyl, aryl, substituted aryl, or an inert group, wherein any two neighboring R , R , R , R , R , R , and R groups taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, wherein R'-R ⁷ other than hydrogen, optionally contain at least one heteroatom; X in Formula (I) is an anion; X in Formula (II) is an anion or an oxygen atom, and n = 1 -3 including non-integers.

In another aspect, the present invention provides a process for the hydrosilylation of a composition containing a silylhydride and a compound containing at least one unsaturated ™· ^,,η ^ocess comprising: reacting a substrate silylhydride with a compound containing at least one unsaturated group in the presence of an activating silylhydride, a promoter compound, and a metal complex to produce a hydrosilylation product containing said complex and/or derivatives thereof,

wherein the metal complex is chosen from a complex of Formula (I), Formula (II), or a combination thereof; where Formula (I) is:

Formula (I);

Formula (II) is: GXn; G is Mn, Fe, i, Ru, or Co; each occurrence of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , is independently H, CI- 18 alkyl, CI -CI 8 substituted alkyl, aryl, substituted aryl, or an

1 2 3 4 5 0

inert group, wherein any two neighboring R , R , R , R , R , R , and R groups taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, wherein R'-R ⁷ other than hydrogen, optionally contain at least one heteroatom; X in Formula (I) is an anion; X in Formula (II) is an anion or an oxygen atom, and n = 1 -3 including non-integers.

In still another aspect, the present invention is directed to a process for the hydrosilylation of a composition containing a silylhydride and a compound containing at least one unsaturated group, the process comprising: (i) providing a mixture comprising a silylhydride, a compound containing at least one unsaturated group, and a complex according to Formula (I); (ii) contacting said mixture with an activating silylhydride and a promoter compound, optionally in the presence of a solvent, to cause the substrate silylhydride to react with the compound containing at least one unsaturated group to produce a hydrosilylation product containing said complex and/or derivatives thereof, and (iii) optionally removing the complex and/or derivatives thereof from the hydrosilylation product, wherein Formula (I) is:

wherein G is Mn, Fe, Ni, Ru, or Co; each occurrence of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , is independently H, Cl-18 alkyl, CI -CI 8 substituted alkyl, aryl, substituted aryl, or an inert group, wherein any two of R , R , R , R , R , R , R taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, wherein R'-R ⁷ other than hydrogen, optionally contain at least one heteroatom.

In yet another aspect, the present invention is directed to a process for the

hydrosilylation of a composition containing a silylhydride and a compound containing at least one unsaturated group, the process comprising: (i) providing a mixture comprising a silylhydride, a compound containing at least one unsaturated group, and a complex according to Formula (II); (ii) contacting said mixture with an activating silylhydride and a promoter compound, optionally in the presence of a solvent, to cause the substrate silylhydride to react with the compound containing at least one unsaturated group to produce a hydrosilylation product containing said complex and/or derivatives thereof, and (iii) optionally removing the complex and/or derivatives thereof from the hydrosilylation product, wherein Formula (II) is GXn, where G is Fe, Ru, Ni, Mn, or Co; X is an anion or an oxygen atom, and n = 1-3 including non-integers.

DETAILED DESCRIPTION OF THE INVENTION

It has now been surprisingly found that various metal salts and metal compounds can be activated in-situ by a silylhydride to generate effective catalysts for the hydrosilylation of an unsaturated hydrocarbon with the same or different silylhydride or a siloxyhydride. The in-situ activation permits a user to control exactly when the reaction occurs, dramatically facilitates the activation process, and utilizes a significantly milder activating agent. This level of control can aid in the commercial production of materials made by the process, as ™ ⁱⁱ ^""istream use of the products in applications. As used herein, "in-situ" is intended to include, but is not limited to, the following situations: (1) the metal based complex, salt or compound of Formula (I) and (II) activated by contacting the metal-based precursor and promoter with a silylhydride when the precursor is present in the reaction mixture of the unsaturated compound and the silylhydride; and (2) the metal based complex, salt or compound of Formula (I) and (II) activated by contacting the metal precursor and promoter with the activating silylhydride to provide an admixture shortly before the admixture contacts the substrate silylhydride and the unsaturated compound. By "shortly before" is meant a time period of less than 24 hours, preferably less than 2 hours, more preferably, less than 30 minutes depending upon the properties of the particular catalyst precursor and the activating silylhydride and promoter used.

As used herein, an "activating silylhydride" is an organosilane or alkoxysilane with at least one SiH unit that, especially in the presence of the promoter, causes a metal salt, compound or complex, to catalyze a hydrosilylation reaction. The efficacy of an activating silylhydride can be determined through experimentation by those skilled in the art.

As used herein, by "unsaturated" is meant one or more double or triple bonds. In a preferred embodiment, it refers to carbon-carbon double or triple bonds.

The process comprises reacting a substrate silylhydride and a compound containing at least one unsaturated group in the presence of an activating silylhydride, a promoter compound, and a metal complex to form a hydrosilylation product comprising the complex and/or derivatives thereof. The metal complex is chosen from a complex of Formula (I), Formula (II), or a c

Formula (I);

GXn Formula (II).

In Formulas (I) and (II), G is Mn, Fe, Ni, Ru, or Co in any of their respective valence states. Each occurrence of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ is independently chosen from H, CI -18 alkyl, CI -CI 8 substituted alkyl, aryl, substituted aryl, or an inert group, wherein any two

" ^ω; " ^{1 Κ} " ^, - ^; "" R , R , R , R , R , R , and R groups taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, wherein R'-R ⁷ other than hydrogen, optionally contain at least one heteroatom.

In Formula (I), X is an anion. In Formula (II), X is an anion or an oxygen atom, and n = 1-3 including non- integer numbers. Where X represents an oxygen atom, GX _n may represent an oxide or mixed oxide of the metal G. It will be further understood that the formula of the metal oxide or mixed oxide will vary based on the nature of the metal and the oxidation state(s). For example, iron oxides may be represented variously as FeO, Fe ₂ 0 ₃ , or Fe ₃ 0 ₄ (FeOFe ₂ 0 ₃ ). In one embodiment, G is Fe, such as Fe (II) or Fe (III). In one embodiment, X in Formula (I) or (II) is an anion, such as a halogen (F ^~ , CI ^" , Br ^" , Γ), chelating oxygen containing ligand such an enolate, acetylacetonate, CF ₃ R ⁸ S0 ₃ ^_ or R ⁹ COO ^" , wherein R ⁸ is a covalent bond or a C1-C6 alkylene group optionally containing one or more heteroatoms, and R ⁹ is a C1-C20 substituted or unsubstituted hydrocarbyl group optionally containing one or more heteroatoms. In one embodiment, X is R ⁹ COO ^" .

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 substrate silylhydride, compound containing at least one unsaturated group, activating silylhydride, promoter, and metal complex/salt can be added together in one solution and then reacted. In another embodiment, the process comprises providing a first mixture comprising the metal complex/salt, promoter, and activating silylhydride, and adding a solution of the substrate silylhydride and unsaturated compound to the first mixture. In still another embodiment, the process comprises providing a first mixture of the metal salt, promoter, activating silylhydride, and substrate silylhydride, and subsequently adding the unsaturated compound to the first mixture. In still another embodiment, the process comprises providing a first mixture of the metal salt, promoter, activating silylhydride, and unsaturated compound, and subsequently adding the substrate silylhydride to the first mixture. 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.

In a further embodiment, the process may comprise providing a first mixture comprising the metal complex/salt, promoter, and activating silane and heating the first mixture; adding the unsaturated compound to the first mixture to form a second mixture, and subsequently adding the substrate silylhydride to the second mixture. In still another further embodiment, the process may comprise providing a first mixture comprising the metal complex/salt, promoter, and activating silylhydride and heating the first mixture; adding the substrate silylhydride to the first mixture to form a second mixture, and subsequently adding the unsaturated compound to the second mixture.

As indicated above, in one embodiment, the present invention is directed to a process for the hydrosilylation of a composition containing a silylhydride and a compound containing at least one unsaturated group, the process comprising: (i) providing a mixture comprising a silylhydride, a compound containing at least one unsaturated group, and a complex according to Formula (I) and/or Formula (II); (ii) contacting said mixture with an activating silylhydride and a promoter compound, optionally in the presence of a solvent, to cause the substrate silylhydride to react with the compound containing at least one unsaturated group to produce a hydrosilylation product containing said complex and/or derivatives thereof, and (iii) optionally removing the complex and/or derivatives thereof from the hydrosilylation product.

It will also be appreciated that, as previously described, the silylhydride employed to activate the metal complex can be the same silylhydride that will react with the unsaturated compound. In such circumstances, the substrate silylhydride and the activating silylhydride can be the same compound, and a single compound can be employed in the process. That is, when the substrate silylhydride is also the activating silylhydride, it is not necessary to utilize separate additions of that material at separate steps in the process.

Non-limiting examples of embodiments of possible hydrosilylation reactions in accordance with the present process are shown schematically in Equation 1 :

^Mes PDIFeCI ₂ + promoter

PhSiH ₃ + octene **PhSioctylH ₂ „ , ° Equation 1.

PhSiH ₃ + octene ^GX " ^{+ promoter} » PhSioctylH _{2 π} .

° Equation 2.

In the embodiments illustrated in Equations 1 and 2, PhSiH ₃ functions as both the substrate silylhydride and the activating silylhydride.

The methods to prepare the catalyst precursors of the present invention are known to a person skilled in the field. The complex of Formula (I) can be prepared by reacting a PDI ligand with a metal halide, such as FeBr ₂ . 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.

An exemplary method to prepare the complex of Formula (I) can be found in

Organometallics (2010), 29(5), 1168-1173 to Zhang et al.

A wide variety of promoters can be employed in the catalyst activation step. Though not wishing to be bound by any theory or mechanism, the promoter will have a high affinity for coordination to a silicon hydride compound and is able to promote the in-situ formation of a hypercoordinate silicon species. (See, Corriu et al. Chem. Rev., 1993, 93, 1371-1448). Promoters useful in the method of the invention include neutral or ionic compounds selected from the groups consisting of amines, imines, carboxylates, ethers, alcohols, ketones, heterocyclics, and other N and/or O-containing species, or mixtures of two or more thereof. These species may be mono-dentate or multi-dentate. Specific examples of promoters include, but are not limited to, 2,6-pyridine(di)imine type compounds such as, for example, ( ^Mes PDI), tetramethylethylenediamine (TMEDA), triethanolamine, lithium acetylacetonate (Liacac), sodium acetate (NaOAc),

tetrabutylammonium fluoride (TBAF), o-aminophenol, diacetylpyridine, dimethanolpyridine, phosphines, pinacol, and imidazole. Preferably, the promoter is compatible and does not react with the substrates for the hydros ilylation reaction. In particular, it is desired that the promoter does not catalyze the disproportionation of alkoxysilanes. The promoter ^Mes PDI, for example, does not disproportionate alkoxysilanes such as triethoxysilane.

The reaction components can optionally be disposed in a solvent. The solvent is not limited and can be either polar or non-polar. Any solvent can be used in the method of the invention, as long as it facilitates the activation and the reaction, without deleterious effects. It is not necessary that the complex of Formula (I) or the salt of Formula (II) be dissolved in any mixture to which it is added (e.g., to a mixture of solvent, substrate, promoter mixture, etc.) before the addition of the other components to that mixture.

The metal species of Formulae (I) and (II) can be activated in-situ to generate reactive catalysts effective at selectively catalyzing industrially practiced hydrosilylation reactions. Accordingly, the catalyst precursors of the invention have utility in the preparation of useful silicone products, including, but not limited to, coatings such as release coatings, room temperature vulcanizates, sealants, adhesives, products for agricultural and personal care applications, silicone surfactants for stabilizing polyurethane foams and silyl- or silicone - modified organic polymers.

When used as catalyst precursors for the hydrosilylation reaction, the complexes of Formula (I) can be supported or immobilized on a support material, for example, carbon, silica, alumina, MgC^ or zirconia, or on a polymer or prepolymer, for example polyethylene, polypropylene, polystyrene, or poly(aminostyrene). The metal complexes can also be supported on dendrimers.

In some embodiments, for the purposes of attaching the catalyst precursors of the invention to a support, it is desirable that at least one of R ¹ to R ⁷ of the metal complexes, 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.

In certain embodiments, silica supported catalyst precursors 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. In some embodiments, the catalyst precursors can be immobilized on the surface of dendrimers 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.

The temperature range for the process of the hydros ilylation is from -50 °C to 250 °C, preferably from -10 °C to 150 °C. The silylhydride and the compound having at least one unsaturated group are typically mixed in a molar ratio ranging from about 0.5:2 to about 1 :0.8, preferably from about 0.8: 1.3 to about 1 :0.9, and most preferably in a molar ratio of 1 : 1 of the reactive groups. The molar ratio of the activating silylhydride with respect to the catalyst precursor is between about 1000: 1 and 1 : 1, preferably between about 100: 1 and 10: 1. The molar ratio of the promoter with respect to the catalyst precursor is between 1000: 1 and 1 : 1, preferably between 10: 1 and 1 : 1. The amount of catalyst in the reaction mixture calculated on ppm level of the metal in the total mass of the mixture is 1 - 10,000 ppm, 10- 5000 ppm, even 20-2000 ppm. For an in-situ activation, a nitrogen atmosphere is particularly suitable.

The silylhydride employed in the hydros ilylation reaction is not particularly limited. It can be any compound selected from the group consisting of R ¹⁰ _a SiH ₄ _ _a , (R ¹⁰ O) _a SiH ₄ _ _a , QuT _v Tp ^H D _w D ^H _x M ^H _y M _z , and combinations of two or more thereof. The silylhydride can contain linear, branched or cyclic structures, or combinations thereof. As used herein, each occurrence of R ¹⁰ is independently CI -CI 8, preferably CI -CIO, more preferably C1-C6 alkyl, CI -CI 8, preferably CI -CIO, more preferably C1-C6 substituted alkyl, wherein R ¹⁰ optionally contains at least one heteroatom, each occurrence of a independently has a value from 1 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 1000, provided that p + x + y equals 1 to 3000 and the valences of the all the elements in the silylhydride 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.

As used herein, an "M" group represents a monofunctional group of formula

R ⁿ 3Si0 _1/2 , a ' Ό" group represents a difunctional group of formula R ⁿ ₂ Si0 ₂ /2, a "T" group *· ^ω "*· ^ωοω " ^+ο " trifunctional group of formula R ⁿ Si03/2, and a "Q" group represents a tetrafunctional group of formula S1O4/2, an "M ^H " group represents HR ⁿ ₂ SiOi _/2 , a "T ^H " represents HS1O3/2, and a "D ^H " group represents R ⁿ HSi02/2. Each occurrence of R ¹¹ is independently CI -CI 8, preferably CI -CIO, more preferably C1-C6 alkyl, CI -CI 8, preferably CI -CIO, more preferably C1-C6 substituted alkyl, wherein R ¹¹ optionally contains at least one heteroatom.

The activating silylhydride can, in embodiments, be chosen from a primary silane, a tertiary silane, or combinations thereof. Examples of compounds that are particularly suitable as activating silylhydrides include, but are not limited to, PhSiH ₃ , octylsilane, triethoxysilane, etc.

In one embodiment, the substrate silylhydride is also the activating silylhydride for the purpose of the reaction. In embodiments where the substrates silylhydride is also the activating silylhydride, the process does not require separate additions of that material to the system. For example, it is sufficient to provide that substrate/activating silylhydride to a particular mixture to carry out the process.

The compound containing an unsaturated group employed in the hydrosilylation reaction includes, but is not limited to, unsaturated polyethers such as alkyl-capped allyl polyethers, vinyl functionalized alkyl capped allyl or methallyl polyether; terminally unsaturated amines; alkynes; C2-C18 olefins, preferably alpha olefins; internal olefins;

unsaturated cycloalkyl epoxide such as vinyl cyclohexyl epoxide; terminally unsaturated acrylates or methyl acrylates; unsaturated aryl ethers; unsaturated aromatic hydrocarbons; unsaturated cycloalkanes such as trivinyl cyclohexane; unsaturated esters and acids; vinyl- functionalized polymer or oligomer; alkenyl-functional silanes, an alkenyl-functional silicones, and vinyl-functionalized silanes and vinyl-functionalized silicones.

Unsaturated polyethers suitable for the hydrosilylation reaction preferably are polyoxyalkylenes having the general formula:

R ¹² (OCH ₂ CH ₂ ) _z (OCH ₂ CHR ¹⁴ ) _w -OR ¹³ (Formula III) or

R ¹³ 0(CHR ¹⁴ CH ₂ 0) _w (CH ₂ CH ₂ 0) _z -CR ¹⁵ ₂ -C≡C-C ¹⁵ ₂ -(OCH ₂ CH ₂ ) _z (OCH ₂ CHR ¹⁴ ) _w R ¹⁶ (Formula IV) or

H ₂ C=CR ¹⁵ CH ₂ 0(CH ₂ CH ₂ 0 ) _z (CH ₂ CHR ¹⁴ 0) _w CH ₂ CR ¹⁵ =CH ₂ (Formula V) wherein R ¹² denotes an unsaturated organic group containing from 2 to 10 carbon atoms such as allyl, methallyl , propargyl or 3-pentynyl. When the unsaturation is olefinic, it is desirably terminal to facilitate smooth hydrosilylation. However, when the unsaturation is a triple ^{1 1} be internal. R ¹³ is vinyl, or a polyether capping group of from 1 to 8 carbon atoms such as the alkyl groups: CH ₃ , n-C ₄ H ₉ , t-C ₄ H ₉ or i-Cstln, the acyl groups such as CH ₃ COO, t-C ₄ H ₉ COO, the beta-ketoester group such as CH ₃ C(0)CH ₂ C(0)0, or a trialkylsilyl group. R ¹⁴ and R ¹⁵ 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 groups, for example, benzyl, phenylethyl and nonylphenyl, or the cycloalkyl groups, for example, cyclohexyl and cyclooctyl. R ¹⁵ may also be hydrogen. Methyl is the most preferred R ¹⁴ and R ¹⁵ groups. R ¹⁶ is vinyl, or a polyether capping group of from 1 to 8 carbon atoms as defined herein above for R ¹³ . 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.

The metal complexes of the invention can also be used in a process for preparing a silylated polyurethane, which includes the step of contacting a terminally unsaturated polyurethane polymer with a silylhydride in the presence of an in-situ activated complex of Formula (I) or (II).

After being activated by the activating silylhydride and promoter, the species formed from Formula I and II are efficient and selective in catalyzing hydros ilylation reactions. For example, when the metal complexes of the invention are employed in the hydrosilylation of an alkyl -capped allyl polyether 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.

Accordingly, in some embodiments, the present invention is also directed to the compositions produced from the above described methods. These compositions contain the hydrosilylated products of the silylhydride and the compound having at least one unsaturated group plus derivatives from the activating agents. The hydrosilylated products that are produced by the process of the present invention have uses in the synthesis of silicone materials such as silanes, adhesives, products for agricultural and personal care applications, and silicone surfactant for stabilizing polyurethane foams.

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 patents, other publications, and U.S. patent applications referred to in the instant application are incorporated herein by reference in their entireties. EXAMPLES

General Considerations:

All air and moisture-sensitive manipulations were carried out using a standard vacuum line, Schlenk, and cannula techniques or in an inert atmosphere drybox containing an atmosphere of purified nitrogen. Methoxypolyethyleneglycolallylether substrate having an average molecular weight of 450 was obtained from NOF Corporation, and sold under the trade name UNIOX PKA5008. All other material was purchased from Aldrich. Solvents and substrates for air and moisture-sensitive manipulations were initially dried and deoxygenated before use. The preparation of PDIFeCl ₂ complexes is known to people skilled in the art. The ¾, ¹³ C and ²⁹ Si NMR spectra were recorded on a Bruker 200 mHZ and 400 mHz spectrometers. GC analysis was performed using a Aligent 7890A gas chromatograph.

The following abbreviations and terms are used: GC, Gas Chromatography; MS, Mass Spectroscopy; THF, tetrahydrofuran; NMR, Nuclear Magnetic Resonance.

Example 1 : Hydrosilylation of 1-Octene with Phenylsilane (PhSiH ₃ ) using ^Mes PDIFeCl?_as a Catalyst Precursor

A vial was charged with ^Mes PDIFeCl ₂ (0.006 g, 0.010 mmol) and purged with nitrogen. A stock solution of ^Mes PDI in THF (1 mL, 29 mM, 0.03 mmol), PhSiH ₃ (0.4 mL,

0.0032 mol) and octene (0.5 mL, 0.0032 mol) were added to the vial. The reaction was stirred at room temperature for 20 hr. The material was exposed to air, filtered and submitted for analysis. In a first control example, a reaction was performed similarly to the above, except 1 mL of THF was added instead of the ^Mes PDI stock solution. In a second control example, a reaction was performed similarly to the above, except without the addition of the

^Mes PDIFeCl ₂ . The results of these examples are shown in Table 1.

Table 1 : Hydrosilylation of 1 -Octene with Phenylsilane (PhSiH ₃ ) using ^Mes PDIFeCl ₂ as a Catalyst Precursor

*Yield of PhSioctylH ₂ was determined by ^zy Si NMR.

Example 2: Hydrosilylation of 1 -Octene with Phenylsilane (PhSiH ) using Iron Stearate

as a Catalyst Precursor

A vial was charged with iron (II) stearate (0.002 g, 0.003 mmol). In a nitrogen filled glovebox, a stock solution of ^Mes PDI in THF (1 mL, 9.6 mM, 0.01 mmol), PhSiH ₃ (0.4 mL, 0.0032 mol) and octene (0.5 mL, 0.0032 mol) were added to the vial. The reaction was heated to 60°C for 1 h. The material was exposed to air, filtered and submitted for analysis. In a first control example, a reaction similar to the above was performed, except 1 mL of THF was added instead of the ^Mes PDI stock solution. In a second control example, a reaction similar to above was performed except without the addition of the iron stearate. The results of these examples are shown in Table 2.

Table 2: Hydrosilylation of 1 -Octene with Phenylsilane (PhSiHs) using Iron Stearate as a Catalyst Precursor

Examples 3-19: Hydrosilylation of 1 -Octene with Phenylsilane (PhSiLL) using a Metal Salt

as a Catalyst Precursor and ^Mes PDI as a promoter

In a nitrogen filled glovebox, a vial was charged with the metal salt (0.01 1 mmol). A stock solution of ^Mes PDI in THF (1 mL, 35 mM, 0.035 mmol), PhSiH ₃ (0.4 mL, 0.0032 mol) and octene (0.5 mL, 0.0032 mol) were added to the vial. The reaction was heated to 60°C for 5 h. The material was exposed to air, filtered and submitted for analysis. The results are shown in Table 3.

Table 3 : Hydrosilylation of 1 -Octene with Phenylsilane (PhSiHs) with Metal Salts as a Catalyst Precursor and ^Mes PDI as a Promoter

12 Manganese (III) acetylacetonate 51

13 Iron (II) oxalate 0

14 Iron (III) tartrate 0

15 Copper (I) chloride 0

16 Copper (II) chloride 0

17 Copper (II) acetate 0

18 Zinc (II) chloride 0

19 Zinc (II) acetate 0

* Yield of PhSioctyffl [ ₂ was determined by ^2y Si NMR.

Example 20: Hydrosilylation of Octene with Phenylsilane (PhSiHQ using a Metal Salt as a

Catalyst Precursor and ^es PDI as a promoter

Experiments with metal salts were run similar to what is described in Example 3. The reactions were run with either 1-octene or 2-octene as the unsaturated substrate as indicated in the table below. The ratio of the terminal and internal addition products (Products A and B) from the hydrosilylation was determined. The results are shown in Table 4.

Product A Product B

Table 4. Hydrosilylation of Octene with Phenylsilane (PhSiHQ using a Metal Salt as a

Catalyst Precursor and ^Mes PDI as a promoter

Examples 21-24: Hydrosilylation of 1 -Octene with Phenylsilane (PhSiH ). with Iron Stearate used as a Catalyst Precursor and ^R PDI as Promoter

The examples below were run in a similar manner except that the reactions were run with 1 mL THF, 1 mL toluene, or neat as indicated in the table below. A vial was charged with the iron (II) stearate (0.004g, 0.006 mmol) and the PDI additive (0.019 mmol). In a nitrogen filled glovebox, the vial was charged with toluene (1 mL), PhSiH ₃ (0.4 mL, 0.0032 mol) and octene (0.5 mL, 0.0032 mol). The reaction was heated to 80°C. Aliquots of the reaction mixture were taken periodically and tested by GC. After the reaction was judged complete by GC, the material was exposed to air, filtered and submitted for analysis. The results are shown in Table 5.

Table 5. Hydrosilylation of 1-Octene with Phenylsilane (PhSiHs), with Iron Stearate used as a

Catalyst Precursor and ^R PDI as Promoter

* Yield of PhSioctylH ₂ was determined by ^2y Si NMR.

i ^Pr2 PDI

Examples 25-34: Hydrosilylation of 1-Octene with an silylhydride, with Iron Stearate used

as a Catalyst Precursor and a ^es PDI Promoter

A vial was charged with the iron (II) stearate (0.002g, 0.003 mmol). In a nitrogen filled glovebox, the vial was charged with a stock solution of ^Mes PDI in THF (1 mL, 10 mM, 0.010 mmol), silylhydride (0.032 mol), octene (0.5 mL, 0.032 mol). The reaction was heated to 60°C for 5h. The results are shown in Table 6. All examples were run similarly except that the reactions were run with 1 mL THF, 1 mL toluene, or neat as indicated in the table below.

Table 6: Hydrosilylation of 1-Octene with an Organosilane, with Iron Stearate used as a

Catalyst Precursor and a PDI Promoter 27 PhSiH ₃ neat 92%

28 OctylSiH ₃ THF 50%

29 OctylSiH3 toluene 0%

30 Me(EtO) ₂ SiH THF 53%

31 Me(EtO) ₂ SiH toluene 3%

32 Me(EtO) ₂ SiH neat 61%

33 Si(OEt) ₃ H toluene 25%

34 Si(OEt) ₃ H neat 27%

*% Yield is given for the mono-hydrosilylated product determined by Si NMR Examples 35-74. Hydrosilylation of 1-octene with phenylsilane (PhSiHQ using iron stearate

as a catalyst precursor and various promoters

A vial was charged with iron (II) stearate (0.004 g, 0.006 mmol) and an additive (0.018 mmol). In a nitrogen filled glovebox THF (2 mL), PhSiH ₃ (0.8 mL, 0.0064 mol) and octene (1.0 mL, 0.0064 mol) were added to the vial. The reaction was heated to 60°C for 5 h. The material was exposed to air, filtered and submitted for analysis.

OEP TPP ^lmpy Example 73 : Hydrosilylation of 1-Octene with Methylbis(trimethylsiloxy)silane (MD ^H M). with PhSiH used as a Activating Silylhydride, Iron Stearate as a Catalyst Precursor and ^Mes PDI as a Promoter. A vial was charged with the iron (II) stearate (0.008g, 0.013 mmol) and the ^Mes PDI additive (0.0153g, 0.039 mmol). In a nitrogen filled glovebox, the vial was charged with THF (1 mL) and PhSiH ₃ (0.25 mL, 0.002 mol). The reaction was heated to 60°C for 1 h to afford a brown solution. A second vial was charged with octene (0.5 mL, 0.0032 mol) and MD ^H M (0.86 mL, 0.0032 mol). To the second vial, 0.25 mL of the brown solution was added. The material was heated to 60°C for an additional hour. The material was exposed to air, filtered and submitted for analysis. The product was recovered in >80% yield.

Example 74: Hydrosilylation of 1 -Octene with Triethoxysilane, with PhSiH used as a

Activating Silylhydride, Iron Stearate as a Catalyst Precursor and ^Mes PDI as a Promoter

A vial was charged with the iron (II) stearate (0.008g, 0.013 mmol) and the ^Mes PDI additive (0.0153g, 0.039 mmol). In a nitrogen filled glovebox, the vial was charged with THF (1 mL) and PhSiH ₃ (0.25 mL, 0.002 mol). The reaction was heated to 60°C for 1 h to afford a brown solution. A second vial was charged with octene (0.5 mL, 0.0032 mol) and Si(OEt) ₃ H (0.59 mL, 0.0032 mol). To the second vial, 0.25 mL of the brown solution was added. The material was heated to 60C for an additional hour. The material was exposed to air, filtered and submitted for analysis. The octylSi(OEt) ₃ product was recovered in >90% yield.

Example 75: Hydrosilylation of Methyl-Capped Allyl Polyether with MD"M, with PhSiH uusseedd aass aann AAcctivator and Iron Stearate as a Catalyst Precursor and ^es PDI used as a Promoter A vial was charged with the iron (II) stearate (0.015g, 0.024 mmol) and the PDI additive (0.029g, 0.072 mmol). In a nitrogen filled glovebox, the vial was charged with THF (1 mL) and PhSiH ₃ (0.25 mL, 0.002 mol). The reaction was heated to 60°C for 1 h to afford a brown solution. A second vial was charged with methyl-capped allyl polyether substrate (PKA5008, 0.0032 mol) and MD ^H M (0.0032 mol). To the second vial, 0.25 mL of the brown solution was added. The material was heated to 60C for an additional 5 hour. The material was exposed to air, filtered and submitted for analysis. The product was recovered in >40%