JP6125222B2 - Dehydrogenated silylation and crosslinking using cobalt catalysts - Google Patents

Description

  The present invention relates to transition metal-containing compounds, and more particularly to pyridinedi-imine ligand-containing cobalt complexes and their use as efficient dehydrogenation silylation catalysts and crosslinking catalysts.

Hydrosilylation chemistry typically involving reactions between silylhydrides and unsaturated organic groups has led to many addition cure products such as silicone surfactants, silicone fluids and silanes and sealants, adhesives and silicone-based coating products. This is the basis of the synthetic route for the production of commercial silicone products such as See, for example, US Patent Application Publication 2011/0009573 A1 by Delis et al. A typical hydrosilylation reaction uses a noble metal catalyst to catalyze the addition of silyl-hydride (Si-H) to unsaturated groups such as olefins. In these reactions, the resulting product is a silyl substituted and saturated compound. In many of these cases, the addition of the silyl group proceeds according to the anti-Markovnikov rule, that is, it adds to the more unsubstituted carbon atom of the unsaturated group. Many noble metal catalyzed hydrosilylations work better with terminally unsaturated olefins, and internal unsaturation is generally either non-reactive or poor reaction only. There are only limited methods for the general hydrosilylation of olefins, and after the addition of Si-H groups, the substrate substrate unsaturation still remains. This reaction is called dehydrogenation silylation and can be used in the synthesis of new silicone materials such as silanes, silicone fluids, crosslinked silicone elastomers and silylated or silicone crosslinked organic polymers such as polyolefins, unsaturated polyesters. There is sex.

Various noble metal complex catalysts are known in the art. For example, US Pat. No. 3,775,452 discloses a platinum complex containing an unsaturated siloxane as a ligand. This type of catalyst is known as Karstedt's catalyst. Other exemplary platinum-based hydrosilylation catalysts described in the literature are Ashby's catalyst disclosed in US Pat. No. 3,159,601, Lamoreaux's catalyst disclosed in US Pat. No. 3,220,972, Speier. , J .; L, Webster, J.A. A. And Barnes, G .; H. J. et al. Am. Chem. Soc. 79, 974 (1957).

There are examples of the use of Fe (CO) ₅ to promote limited hydrosilylation and dehydrogenation silylation (Nesmeyanov, AN; Fredlina, R. Kh .; Chukovskaya, EC; Petrov, R. G .; Belyavsky, AB Tetrahedron, 1962, 3, 371 and Marciniec, B .; see Majchrzak, M. Inorg. Chem. Commun. 2000, 3, 371). It has been found that the use of Fe ₃ (CO) ₁₂ indicates dehydrogenation silylation in the reaction of Et ₃ SiH with styrene (Kakiuchi, F; Tanaka, Y .; Chatani, N .; Murai, S .; J. Organomet. Chem. 1993, 456, 45). Also, several cyclopentadiene iron complexes have been used with varying degrees of success in Nakazawa's work and are of interest for intramolecular dehydrogenated silylation / hydrogenation when used with 1,3-di-vinyldisiloxane. (Roman N Namov, Masumi Itazaki, Masahiro Kamitani and Hiroshi Nakazawa, Journal of the American Chemical Society, 2012, 134, 2801).

  Rhodium complexes have been found to provide low to moderate yields of allyl silane and vinyl silane (Doyle, MP; Devora GA; Nevado, AO; High, KG). Organometallics, 1992, 11, 540-555). Iridium complexes have been found to yield vinylsilanes in good yields (Falck, JR; Lu, B. J. Org Chem, 2010, 75, 1701-1705). Allylsilanes can be prepared in high yields using rhodium complexes (Mitsudo, T .; Watanabe, Y .; Hori, Y. Bull. Chem. Soc. Jpn. 1988, 61, 3011-3013). Vinyl silanes can be prepared by use of rhodium complexes (Murai, S .; Kakiuchi, F .; Nogami, K; Chatani, N .; Seki, Y. Organometallics, 1993, 12, 4748-4750). Dehydrogenation silylation has been found to occur when using iridium complexes (Oro, LA; Fernandez, MJ; Estuelas, MA; Jiminez, MS J. Mol). Catalysis, 1986, 37, 151-156 and Oro, LA; Fernandez, M.J .; Esteruelas, MA; Jiminez, MS Organometallics, 1986, 5, 1519-1520). Vinylsilanes can be prepared using ruthenium complexes (Murai, S .; Seki, Y .; Takeshita, K .; Kawamoto, K .; Sonoda, N. J. Org. Chem. 1986, 51, 3890-3895).

  Recently, a palladium-catalyzed silyl Heck reaction has been reported to result in the formation of allyl silane and vinyl silane (McAtee JR et al., Angelwandte Chemie, International Edition in England, March 1, 2012).

  US Pat. No. 5,955,555 disclosed the synthesis of certain iron or cobalt pyridine-diimine dianion complexes. Preferred anions are chloride, bromide and tetrafluoroborate. US Pat. No. 7,442,819 discloses iron and cobalt complexes of certain tricyclic ligands containing a “pyridine” ring substituted with two imino groups. US Pat. No. 6,461,994, US Pat. No. 6,657,026 and US Pat. No. 7,148,304 disclose several catalyst systems containing specific transition metal-PDI complexes. US Pat. No. 7,053,020 discloses a catalyst system containing, inter alia, one or more bisaryliminopyridine iron or cobalt catalysts. However, the catalysts and catalyst systems disclosed in those references describe use in the process of olefin polymerization and / or oligomerization, but not in the process of dehydrosilylation reactions.

  There remains a need in the silylation industry for non-noble metal based catalysts that are useful in efficiently and selectively catalyzing dehydrogenation silylation. The present invention provides a solution to that need.

の錯体もしくはその付加物であり、
式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５の各々は独立して、水素、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリール、置換アリール、もしくは不活性官能基であり、ここで水素以外のＲ^１〜Ｒ^５は、任意選択で少なくとも一つのヘテロ原子を含有し；
Ｒ^６およびＲ^７の各々は独立して、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリールであり、ここでＲ^６およびＲ^７は任意選択で少なくとも一つのヘテロ原子を含有し；
任意選択で、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７の互いに隣接する任意の二つが一緒になって、置換のもしくは不置換の、飽和のもしくは不飽和の環状構造を形成してもよく、
Ｌはヒドロキシルであるかまたは、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリール基、または成分（ａ）〔Ｌは任意選択で少なくとも一つのヘテロ原子を含有する〕である。 In one embodiment, the present invention contains (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silyl hydride functional group, and (c) a catalyst. A process for producing a dehydrogenated silylation product comprising the step of reacting the mixture, optionally in the presence of a solvent, to produce a dehydrogenated silylation product, wherein the catalyst is of the formula (I):

Complex or adduct thereof,
Where
Each 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 functional group, wherein And R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated An annular structure may be formed,
L is hydroxyl or C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, or component (a) [L optionally contains at least one heteroatom].

式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５の各々は独立して、水素、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリール、置換アリール、もしくは不活性官能基であり、ここで水素以外のＲ^１〜Ｒ^５は、任意選択で少なくとも一つのヘテロ原子を含有し；
Ｒ^６およびＲ^７の各々は独立して、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリールであり、ここでＲ^６およびＲ^７は任意選択で少なくとも一つのヘテロ原子を含有し；
任意選択で、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７の互いに隣接する任意の二つが一緒になって、置換のもしくは不置換の、飽和のもしくは不飽和の環状構造を形成してもよい。 In another embodiment, the present invention is directed to a compound of formula (II)

Where
Each 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 functional group, wherein And R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated An annular structure may be formed.

の錯体もしくはその付加物であり、
式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５の各々は独立して、水素、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリール、置換アリール、もしくは不活性官能基であり、ここで水素以外のＲ^１〜Ｒ^５は、任意選択で少なくとも一つのヘテロ原子を含有し；
Ｒ^６およびＲ^７の各々は独立して、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリールであり、ここでＲ^６およびＲ^７は任意選択で少なくとも一つのヘテロ原子を含有し；
任意選択で、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７の互いに隣接する任意の二つが一緒になって、置換のもしくは不置換の、飽和のもしくは不飽和の環状構造を形成してもよく、
Ｌはヒドロキシルであるかまたは、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリール基からなる群より選択されるアニオン性配位子であるか、または成分（ａ）〔Ｌは任意選択で少なくとも一つのヘテロ原子を含有する〕であり、
Ｙは中性の配位子であり、そして
Ｑは非配位性アニオンである。 In another embodiment, the present invention contains (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silyl hydride functional group, and (c) a catalyst. A process for producing a dehydrogenated silylation product comprising the step of reacting the mixture, optionally in the presence of a solvent, to produce a dehydrogenated silylation product, wherein the catalyst is of formula (III):

Complex or adduct thereof,
Where
Each 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 functional group, wherein And R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated An annular structure may be formed,
L is hydroxyl or an anionic ligand selected from the group consisting of C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl groups, or component (a) [L is Optionally containing at least one heteroatom),
Y is a neutral ligand and Q is a non-coordinating anion.

の錯体もしくはその付加物であり、
式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５の各々は独立して、水素、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリール、置換アリール、もしくは不活性官能基であり、ここで水素以外のＲ^１〜Ｒ^５は、任意選択で少なくとも一つのヘテロ原子を含有し；
Ｒ^６およびＲ^７の各々は独立して、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリールであり、ここでＲ^６およびＲ^７は任意選択で少なくとも一つのヘテロ原子を含有し；
任意選択で、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７の互いに隣接する任意の二つが一緒になって、置換のもしくは不置換の、飽和のもしくは不飽和の環状構造を形成してもよく、
Ｌはヒドロキシルであるかまたは、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリール基、または成分（ａ）〔Ｌは任意選択で少なくとも一つのヘテロ原子を含有する〕である。 In another embodiment, the present invention provides (a) a silylhydride-containing polymer, (b) a monounsaturated olefin or unsaturated polyolefin or mixture thereof, (c) a reaction mixture containing a catalyst, optionally in the presence of a solvent. Aimed at a process for producing a cross-linked material comprising reacting to produce a cross-linked material, wherein the catalyst is of formula (I):

Complex or adduct thereof,
Where
Each 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 functional group, wherein And R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated An annular structure may be formed,
L is hydroxyl or C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, or component (a) [L optionally contains at least one heteroatom].

  The present invention relates to cobalt complexes containing pyridine di-imine ligands and their use as catalysts for efficient dehydrogenation silylation and crosslinking. In an embodiment of the invention, there is provided a complex of formula (I), (II) or (III) as described above for use in said dehydrogenation silylation and crosslinking reaction, wherein Co is of any valence Some or any oxidation state (eg, +1, +2, +3). In particular, according to one embodiment of the present invention, a class of cobalt pyridine di-imine complexes has been found capable of dehydrogenation silylation reactions.

  As used herein, “alkyl” is meant to include linear, branched and cyclic alkyl groups. Non-limiting examples of alkyl include, but are not limited to, methyl, ethyl, propyl, and isobutyl.

  As used herein, “substituted alkyl” means an alkyl group that contains one or more substituents, which are inert under the process conditions in which the compound containing those groups is provided. The substituents also do not substantially interfere with the process and do not deleteriously interfere.

  As used herein, “aryl” means, without limitation, any aromatic hydrocarbon group from which one hydrogen atom has been removed. Aryl may contain one or more aromatic rings, which are fused or linked to a single bond or other group. Non-limiting examples of aryl include, but are not limited to, tolyl, xylyl, phenyl and naphthalenyl.

  As used herein, “substituted aryl” means an aromatic group that is substituted as described in the definition of “substituted alkyl” above. Like aryl, substituted aryl may contain one or more aromatic rings, which are fused or attached to a single bond or other group. However, when a substituted aryl has a heteroaromatic ring, the free valence in the substituted aryl group can be a heteroatom of the heteroaromatic ring that substitutes for carbon (such as nitrogen). Unless stated otherwise, it is preferred that substituted aryl groups herein contain 1 to about 30 carbon atoms.

  As used herein, “alkenyl” refers to a linear, branched or cyclic alkenyl group containing one or more carbon-carbon double bonds, where the position of substitution is a carbon-carbon double bond. Or anywhere within the group. Non-limiting examples of alkenyl include, but are not limited to, vinyl, propenyl, allyl, methallyl, ethylidenyl norbornane.

  As used herein, “alkynyl” means any linear, branched or cyclic alkynyl group containing one or more carbon-carbon triple bonds, wherein the position of substitution is at the carbon-carbon triple bond. Or anywhere within the group.

  By “unsaturated” is meant one or more double or triple bonds. In preferred embodiments, it refers to a carbon-carbon bond or a triple bond.

As used herein, “inert functional group” means a group other than hydrocarbyl or substituted hydrocarbyl, which is inert under the process conditions in which the compound containing the group is provided. Inert functional groups also do not substantially interfere with or deleteriously interfere with any process described herein in which compounds with them may participate. Examples of inert functional groups include ethers such as halo (fluoro, chloro, bromo and iodo), —OR ³⁰ [R ³⁰ is hydrocarbyl or substituted hydrocarbyl].

  As used herein, “heteroatom” means any of Group 13-17 elements excluding carbon, and may include, for example, oxygen, nitrogen, silicon, phosphorus, fluorine, chlorine, bromine and iodine.

As used herein, “olefin” means any aliphatic or aromatic hydrocarbon containing one or more aliphatic carbon-carbon unsaturations. Such olefins may be linear, branched or cyclic and may be substituted with the heteroatoms described above, provided that the substitution substantially interferes with the desired course of reaction to produce the dehydrogenated silylation product. And no harmful interference. In one embodiment, the unsaturated compound useful as a dehydrogenation silylation reactant is an organic compound having a structural group, R ₂ C═C—CHR, where R is an organic fragment or hydrogen.

の錯体もしくはその付加物であり、
式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５の各々は独立して、水素、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリール、置換アリール、もしくは不活性官能基であり、ここで水素以外のＲ^１〜Ｒ^５は、任意選択で少なくとも一つのヘテロ原子を含有し；
Ｒ^６およびＲ^７の各々は独立して、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリールであり、ここでＲ^６およびＲ^７は任意選択で少なくとも一つのヘテロ原子を含有し；
任意選択で、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７の互いに隣接する任意の二つが一緒になって、置換のもしくは不置換の、飽和のもしくは不飽和の環状構造を形成してもよく、
Ｌはヒドロキシルであるかまたは、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリール基、または成分（ａ）〔Ｌは任意選択で少なくとも一つのヘテロ原子を含有する〕である。 As mentioned above, the present invention contains (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silyl hydride functional group, and (c) a catalyst. A process for producing a dehydrogenated silylation product comprising the step of reacting the mixture, optionally in the presence of a solvent, to produce a dehydrogenated silylation product, wherein the catalyst is of the formula (I):

Complex or adduct thereof,
Where
Each 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 functional group, wherein And R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated An annular structure may be formed,
L is hydroxyl or C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, or component (a) [L optionally contains at least one heteroatom].

であり、
式中、
Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１およびＲ^１２の各々は独立して、水素、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリール、置換アリール、もしくは不活性官能基であり、ここで水素以外のＲ^８〜Ｒ^１２は、任意選択で少なくとも一つのヘテロ原子を含有する。Ｒ^８およびＲ^１２はさらに、独立してメチル、エチル、もしくはイソプロピル基を含み得、そしてＲ^１０は水素もしくはメチルであってよい。一つの好ましい実施態様において、Ｒ^８、Ｒ^１０およびＲ^１２はそれぞれメチルであり得、Ｒ^１およびＲ^５は独立してメチルもしくはフェニル基であり得、そしてＲ^２、Ｒ^３およびＲ^４は水素であり得る。一実施態様において、触媒は式（ＩＩＩ）の錯体のＭｅＢ（Ｃ_６Ｆ_５）_３ ⁻もしくはテトラキス（パーフルオロアリール）ボラート塩である。 The catalyst used in the process of the present invention is shown in Formula (I) above, where Co is any valence or any oxidation state (eg, +1, +2, +3). In one embodiment, at least one of R ⁶ and R ⁷ is

And
Where
Each of R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group, wherein And R ^{8 to} R ¹² other than hydrogen optionally contain at least one heteroatom. R ⁸ and R ¹² may further independently include a methyl, ethyl, or isopropyl group, and R ¹⁰ may be hydrogen or methyl. In one preferred embodiment, R ⁸ , R ¹⁰ and R ¹² can each be methyl, R ¹ and R ⁵ can independently be methyl or phenyl groups, and R ² , R ³ and R ⁴ are hydrogen It can be. In one embodiment, the catalyst is a MeB (C ₆ F ₅ ) ₃ ^— or tetrakis (perfluoroaryl) borate salt of a complex of formula (III).

の化合物であり、
式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５の各々は独立して、水素、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリール、置換アリール、もしくは不活性官能基であり、ここで水素以外のＲ^１〜Ｒ^５は、任意選択で少なくとも一つのヘテロ原子を含有し；
Ｒ^６およびＲ^７の各々は独立して、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリールであり、ここでＲ^６およびＲ^７は任意選択で少なくとも一つのヘテロ原子を含有し；
任意選択で、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７の互いに隣接する任意の二つが一緒になって、置換のもしくは不置換の、飽和のもしくは不飽和の環状構造を形成してもよい。 One particularly preferred embodiment of the catalyst of the process of the invention is a compound of formula (II)

A compound of
Where
Each 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 functional group, wherein And R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated An annular structure may be formed.

の形状もしくはその付加物であり、
式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５の各々は独立して、水素、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリール、置換アリール、もしくは不活性官能基であり、ここで水素以外のＲ^１〜Ｒ^５は、任意選択で少なくとも一つのヘテロ原子を含有し；
Ｒ^６およびＲ^７の各々は独立して、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリールであり、ここでＲ^６およびＲ^７は任意選択で少なくとも一つのヘテロ原子を含有し；
任意選択で、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７の互いに隣接する任意の二つが一緒になって、置換のもしくは不置換の、飽和のもしくは不飽和の環状構造を形成してもよく、
Ｌはヒドロキシルであるかまたは、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリール基からなる群より選択されるアニオン性配位子であるか、または成分（ａ）〔Ｌは任意選択で少なくとも一つのヘテロ原子を含有する〕であり、
Ｙは中性の配位子であり、そして
Ｑは非配位性アニオンである。 In an alternative embodiment, the catalyst used in the process of the invention is of formula (III):

Shape or its adjunct,
Where
Each 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 functional group, wherein And R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated An annular structure may be formed,
L is hydroxyl or an anionic ligand selected from the group consisting of C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl groups, or component (a) [L is Optionally containing at least one heteroatom),
Y is a neutral ligand and Q is a non-coordinating anion.

As described herein, “neutral ligand” means any ligand that is not charged. “Non-coordinating anion” means an anion that only weakly interacts with a cation. Examples of the non-coordinating anion Q are [B [3,5- (CF ₃ ) ₂ C ₆ H ₃ ] ₄ ] −, B (C ₆ F ₅ ) ₄ ⁻ , Al (OC (CF ₃ ) ₃ ). ₄ -, and _CB 11 _{H 12} - including but not limited to a. Examples of the neutral ligand Y include dinitrogen (N ₂ ), phosphines, CO, nitrosyl, olefins, amines, ethers and the like. Specific examples of Y include, but are not limited to, PH ₃ , PMe ₃ , CO, NO, ethylene , THF, and NH ₃ .

によって表され、
式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５の各々は独立して、水素、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリール、置換アリール、もしくは不活性官能基であり、ここで水素以外のＲ^１〜Ｒ^５は、任意選択で少なくとも一つのヘテロ原子を含有し；
Ｒ^６およびＲ^７の各々は独立して、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリールであり、ここでＲ^６およびＲ^７は任意選択で少なくとも一つのヘテロ原子を含有し；
任意選択で、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７の互いに隣接する任意の二つが一緒になって、置換のもしくは不置換の、飽和のもしくは不飽和の環状構造を形成してもよく、そして
Ｘは、Ｆ⁻、Ｃｌ⁻、Ｂｒ⁻、Ｉ⁻、ＣＦ_３Ｒ^４０ＳＯ_３ ⁻もしくはＲ^５０ＣＯＯ⁻からなる群より選択され、式中、Ｒ^４０は共有結合もしくはＣ１〜Ｃ６のアルキレン基であり、そしてＲ^５０はＣ１〜Ｃ１０のヒドロカルビル基である。
Various methods can be used to prepare the catalyst used in the process of the present invention. In one embodiment, the catalyst comprises at least one component selected from the group consisting of a catalyst precursor and an activator , a solvent, a silyl hydride, a compound containing at least one unsaturated group, and combinations thereof. Can be produced in situ by contacting in the presence of a liquid medium containing, wherein the catalyst precursor has the structural formula (IV)

Represented by
Where
Each 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 functional group, wherein And R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated And X may be selected from the group consisting of F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , CF ₃ R ⁴⁰ SO ₃ ^— or R ⁵⁰ COO ⁻ , wherein R ⁴⁰ is an alkylene group of a covalent bond or C1 -C6, and ^{R 50} is a hydrocarbyl group of C1 -C10.

_{Activator, NaHBEt 3, CH 3 Li,} DIBAL-H, or a reducing agent or an alkylating agent such as LiHMDS, and combinations thereof. Preferably, the reducing agent has a more negative reduction potential than -0.6 V (vs. ferrocene as described in Chem. Rev. 1996, 96, 877-910. Larger negative numbers result in greater reduction Shows potential). Preferably, the reduction potential is in the range of −0.76 to −2.71V. The most preferred reducing agent has a reduction potential in the range of -2.8 to -3.1V.

Methods for preparing catalysts are known to those skilled in the art. For example U.S. as disclosed in Patent Application Publication 2011 / 0009573A1, the catalyst may be prepared by reacting a metal halide such as PDI ligand and FeBr _2. Typically, PDI ligands can be prepared by condensing a suitable amine or aniline with 2,6-diacetylpyridine and its derivatives. If desired, the PDI ligand can be further modified by known aromatic substitution chemistry.

In the process of the present invention, the catalyst is either on a support such as carbon, silica, alumina, MgCl ₂ , or zirconia, or a polymer such as polyethylene, polypropylene, polystyrene, poly (aminostyrene), or sulfonated polystyrene or It may be not supported or fixed on the prepolymer. Metal complexes may also be supported on the dendrimer.

In one embodiment, for the purpose of adhering to support the metal complex of the present invention, at least one of R ^{1 to} R ⁹ of the metal complex, preferably R ⁶ is covalently bonded to the support. It is desirable to have functional groups that are effective. Exemplary functional groups include but are not limited to SH, COOH, NH ₂ or OH groups.

  In one embodiment, the silica-supported catalyst is, for example, Macromol. Chem. Phys. 2001, 202, no. 5, pp. 645-653; Journal of Chromatography A, 1025 (2003) 65-71, and can be prepared by Ring-Opening Metabolization (ROMP) technology as described in the literature.

  One method for immobilizing a catalyst on the surface of a dendrimer is the original dendrimer and functionalized PDI of Si-Cl bonds in the presence of a base, as shown by Kim in Journal of Organometallic Chemistry 673 (2003) 77-83. Is due to the reaction.

  The unsaturated compound containing at least one unsaturated group used in the process of the present invention can be a compound having one, two, three or more unsaturations. Examples of such unsaturated compounds are olefins, cycloalkenes, unsaturated polyethers such as alkyl capped allyl polyethers, vinyl functionalized alkyl capped allyl or methallyl polyethers, alkyl capped terminally unsaturated amines, alkynes, terminal Includes unsaturated acrylates or methacrylates, unsaturated aryl ethers, vinyl functionalized polymers or oligomers, vinyl functionalized silanes, vinyl functionalized silicones, unsaturated fatty acids, unsaturated esters, and combinations thereof.

The unsaturated polyether suitable for the dehydrogenation silylation reaction is preferably of the general formula:
^{_{R 1 (OCH 2 CH 2)}} z (OCH 2 CHR 3) w -OR 2 ( wherein V) or ^{_{R 2 O (CHR 3 CH 2}} O) w (CH 2 CH 2 O) z -CR 4 2 -C≡ ^{_{C-CR 4 2 - (OCH}} 2 CH 2) z (OCH 2 CHR 3) w R 2 ( formula VI) or ^{_{H 2 C = CR 4 CH 2}} O (CH 2 OCH 2) z (CH 2 OCHR 3) w CH ₂ CR ⁴ = CH ₂ (formula VII)
A polyoxyalkylene having
In the formula, R ¹ represents an unsaturated organic group containing 2 to 10 carbon atoms such as allyl, methylallyl, propargyl or 3-pentynyl. When the unsaturation is an olefin, it is preferably terminal to promote smooth dehydrogenation silylation. However, when the unsaturation is a triple bond, it can be internal. R ² is hydrogen, vinyl, or an alkyl group: CH ₃ , n-C ₄ H ₉ , t-C ₄ H ₉ or i-C ₈ H ₁₇ ; acyl such as CH ₃ COO, t-C ₄ H ₉ COO a ketoester groups or 1-8 polyether capping group of carbon atoms, such as trialkylsilyl group, - _{group, CH 3 C (O) CH} 2 C (O) beta, such as O. R ³ and R ⁴ are for example C1-C20 alkyl groups such as methyl, ethyl, isopropyl, 2-ethylhexyl, dodecyl and stearyl, eg aryl groups such as phenyl and naphthyl, eg benzyl, phenylethyl and nonylphenyl. Alkaryl or aralkyl groups or monovalent hydrocarbon groups such as cycloalkyl groups such as cyclohexyl and cyclooctyl. R ⁴ may also be hydrogen. Methyl is the most preferred R ³ and R ⁴ group. Each of z is from 0 to 100 and each of w is from 0 to 100. Preferred values for z and w are 1 to 50.

であり、
式中、Ｒ８の各々は独立してＣ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、ビニル、アリール、もしくは置換アリール、そしてｎは０より大きいかもしくは０と等しい。ここで定義されるとき、「内部オレフィン」は、３−ヘキセンのようにオレフィン基が鎖もしくは分岐の末端に配置されないことを意味する。 Specific examples of preferred unsaturations useful in the process of the present invention include N, N-dimethylallylamine, allyloxy substituted polyethers, propylene, 1-butene, 1-hexene, styrene, vinyl norbornane, 5-vinyl-norbornane, 1- Long chain, straight chain alpha olefins such as octadecene, internal olefins such as cyclopentene, cyclohexene, norbornene and 3-hexene, branched olefins such as isobutylene and 3-methyl-1-octene, such as polybutadiene, polyisoprene and EPDM unsaturated polyolefin, oleic acid, such as, unsaturated acids or esters such as linoleic acid and methyl oleate, includes a vinyl siloxane and combinations thereof of the formula (VIII), wherein formula (VIII)

And
Wherein each R8 is independently C1-C18 alkyl, C1-C18 substituted alkyl, vinyl, aryl, or substituted aryl, and n is greater than or equal to zero. As defined herein, “internal olefin” means that the olefin group is not located at the end of the chain or branch, such as 3-hexene.

The silyl hydride used in the reaction is not particularly limited. R _a SiH _4-a, which may be ^{_{(RO) a SiH 4-a}} , O u T v T p H D w D H x M H y N z and any compound selected from the group consisting of: . Silyl hydrides can contain linear, branched or cyclic structures as well as combinations thereof. As used herein, each of R is independently C1-C18 alkyl, C1-C18 substituted alkyl, wherein R optionally contains at least one heteroatom and each of a Independently has a value of 1 to 3, each of p, u, v, y and z independently has a value of 0 to 20, w and x are 0 to 500, provided that p + x + y is 1 Equal to 500, the values of all elements in the silylhydride are satisfied. Preferably, p, u, v, y and z are from 0 to 10, and w and x are from 0 to 100, where p + x + y is equal to 1 to 100.

As used herein, the “M” group represents a monofunctional group of formula R ′ ₃ SiO _1/2 and the “D” group represents a bifunctional group of formula R ′ ₂ SiO _2/2 and “T Group represents a trifunctional group of formula R′SiO _3/2 and “Q” group represents a tetrafunctional group of formula SiO _4/2 and “M ^H ” group represents H _g R ′ _3-g represents SiO _1/2, ^{"T H"} represents _{HSiO 3/2,} ^{"D H"} represents the R'HSiO _2/2. As used herein, g is an integer from 1 to 3. Each R ′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, wherein R ′ optionally contains at least one heteroatom.

Examples of silyl hydrides containing at least one silyl hydride functional group are R _a SiH _4-a , (RO) _a SiH _4-a , HSiR _a (OR) _3-a , R ₃ Si (CH ₂ ) _f ( SiR ₂ O) _k SiR ₂ H, (RO) ₃ Si (CH ₂ ) _f (SiR ₂ O) _k SiR ₂ H, _Qu T _v T _p ^H D _w D ^H _x M ^H _y M _z and combinations thereof _Where Q is SiO _4/2 , T is R′SiO _3/2 , T ^H is HSiO _3/2 , D is R ′ ₂ SiO _2/2 , D ^H Is R′HSiO _2/2 , ^MH is H _g R ′ _3-g SiO _1/2 , M is R ′ ₃ SiO _1/2 , and each of R and R ′ is independently C1-C18 Of alkyl, C1-C18 substituted alkyl, aryl or substituted aryl Wherein R and R ′ optionally contain at least one heteroatom, each of a independently has a value of 1 to 3, f has a value of 1 to 8, and k has a value of 1 to Has a value of 11, g has a value of 1 to 3, p is 0 to 20, u is 0 to 20, v is 0 to 20, w is 0 to 1000, x is 0 to 1000, y is 0 to 20, and z is 0 to 20, p + x + y is equal to 1 to 3000, and the valences of all elements in the silyl hydride are satisfied Yes. In the above formula, p, u, v, y and z may be from 0 to 10 and w and x may be from 0 to 100, where p + x + y is equal to 1 to 100.

式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５の各々は独立して、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリールであり、Ｒ^６は水素、Ｃ１〜Ｃ１８のアルキル、Ｃ１〜Ｃ１８の置換アルキル、アリールもしくは置換アリールであり、ｘおよびｗは独立して０より大きいかもしくは０と等しく（式Ｘではｘは少なくとも１と等しい）、そしてａおよびｂは０から３の整数であり、ａ＋ｂ＝３であるという条件である。 In one embodiment, the silyl hydride can have one of the following structures:
R ¹ _a (R ² O) _b SiH (Formula IX)

Where
Each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, R ⁶ is hydrogen, C1-C18 Alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, x and w are independently greater than or equal to 0 (in formula X, x is at least equal to 1), and a and b are from 0 The condition is an integer of 3 and a + b = 3.

The catalysts of formula (I, II and III) are useful for catalyzing the dehydrogenation silylation reaction. For example, suitable silylhydrides such as triethoxysilane, triethylsilane, MD ^H M or silylhydride functional polysiloxanes (eg, SL6020 from Momentive Performance Materials., Inc.) are octenes in the presence of Co catalyst, Reacting with monounsaturated hydrocarbons such as dodecene, butene, etc., the resulting product is a terminal silyl-substituted alkene, where the unsaturation is in the beta position relative to the silyl group. A byproduct of the reaction is a hydrogenated olefin. When the reaction is carried out at a 0.5: 1 molar ratio of silane to olefin, the resulting product is formed in a 1: 1 ratio. An example is shown in the reaction diagram below.

The reaction is typically easy at ambient and ambient pressures, but can be carried out at lower or higher temperatures (0 ° C. to 300 ° C.) or lower or higher pressures (ambient to 3000 psi). . A range of unsaturated compounds such as N, N-dimethylallylamine, allyloxy substituted polyethers, cyclohexane, and linear alpha olefins (ie, 1-butene, 1-octene, 1-dodecene, etc.) are utilized in this reaction. it can. When an alkene containing an internal double bond is used, the catalyst can first isomerize the olefin and the resulting reaction product is the same as when a terminal unsaturated alkene is used.

When the reaction is carried out in a 1: 1 silylhydride to olefin ratio, the reaction results in a bis-substituted silane, the silyl group is located at the end of the compound, and there are still unsaturated groups in the product.

When the catalyst is first used to prepare a terminally substituted silylalkene, a second silane can be added to produce the asymmetrically substituted bis-silylalkene. The resulting silane is end-substituted at both ends. This bis-silane can be a useful starting material for the production of alpha, omega-substituted alkanes or alkenes such as diols or other compounds that can be easily derived from silylated products. Long chain alpha, omega-substituted alkanes or alkenes are not easily prepared today and may have a variety of uses for the preparation of proprietary polymers (such as polyurethane) and other useful compounds.

Since the alkene double bonds are preserved during the dehydrogenation silylation reaction using these cobalt catalysts, monounsaturated olefins are used to crosslink silylhydrides containing polymers. For example, silylhydridopolysiloxanes such as SL6020 (MD ₁₅ ^DH ₃₀ M) can react with 1-octene in the presence of the cobalt catalyst of the present invention to produce a cross-linked elastic material. Various new materials can be produced in this way by changing the length of the hydride polymer and the olefin used for crosslinking. Thus, the catalysts used in the process of the present invention include silicone surfactants that stabilize coats such as release coats, room temperature vulcanizates, sealants, adhesives, products for agricultural and personal care applications, and polyurethane foam. Useful for the preparation of useful silicone products, including but not limited to agents.

  In addition, dehydrogenation silylation can be performed on any number of unsaturated polyolefins such as polybutadiene, polyisoprene, EPDM type copolymers, and these commercially important polymers can be silyl grouped at lower temperatures than conventionally used. Functionalize or crosslink them with hydrosiloxanes with multiple SiH groups. This offers the possibility to extend the use of these already valuable materials to newer commercially useful areas.

  In one embodiment, the catalyst is useful for dehydrosilylation of a composition containing silylhydride and a compound containing at least one unsaturated group. The process may include a metal complex catalyst by contacting the compound with a metal complex of a supported or unsupported catalyst and reacting the silyl hydride with a compound having at least one unsaturated group. Including producing no dehydrogenated silylation product. The dehydrogenation silylation reaction can optionally be carried out in the presence of a solvent. If desired, after the dehydrogenation silylation reaction is complete, the metal complex can be removed from the reaction product by magnetic separation and / or filtration. These reactions can be carried out either in a stock solution or diluted in a suitable solvent. Typical solvents include benzene, toluene, diethyl ether and the like. It is preferred to carry out the reaction under an inert atmosphere. The catalyst can be generated in situ by reduction with a suitable reducing agent.

The catalyst complex of the present invention is efficient and selective in catalyzing the dehydrogenation silylation reaction. For example, when the catalyst complex of the present invention is used in dehydrogenated silylation of an alkyl-capped allyl polyether or a compound containing an unsaturated group, the reaction product substantially comprises an unreacted alkyl-capped allyl polyether and its isomerized product. Not included. In one embodiment, the reaction product does not include unreacted alkyl-capped allyl polyether and its isomerized product. Further, when the compound containing an unsaturated group is an unsaturated amine compound , the dehydrogenated silylation product is substantially free of internal addition products, unreacted unsaturated amines and isomerization products of unsaturated amine compounds. As used herein, “substantially free” means less than 10%, preferably less than 5%, based on the total weight of the hydrosilylation product. “Substantially free of internal addition products” means that silicon is added to the terminal carbon.

  The following examples are meant to be illustrative and are not meant to limit the scope of the invention. Unless otherwise stated explicitly, all parts and percentages are on a weight basis and all temperatures are in degrees Celsius. All publications and US patents cited in this application are hereby incorporated by reference in their entirety.

General Considerations All air and moisture sensitive operations were performed using a standard vacuum line Schlenk and cannula technology or in an MBraun inert environment drying box with a purified nitrogen environment. Solvents for air and moisture sensitive manipulations were first dried and deoxygenated using literature procedures (Pangborn, AB et al. Organometallics 15: 1518 (1996)). Chloroform -d and benzene _{d 6} were purchased from Cambridge Isotope Laboratories. Complex ( ^iPr PDI) CoN ₂ (Bowman AC et al., JACS 132: 1676 (2010)), ( ^Et PDI) CoN ₂ (Bowman AC et al., JACS 132: 1676 (2010)), ( ^iPr BPDI) CoN ₂ (Bowman AC et ^{_{al., JACS 132: 1676 (2010)}} ), (Mes PDI) CoCH 3 (Humpheries, MJ Organometallics 24: 2039.2 (2005)), (Mes PDI) CoCl (Humpheries, MJ Organometallics 24: 2039.2 (2005) ^{), [(Mes PDI) CoN} 2] [MeB (C 6 F 5) 3] (Gibson, VC et al., J.Chem.Comm.2252 (2001)), and ^[(Mes PDI) _{oCH 3] [BArF 24] (} Atienza, CCH et, Angew.Chem.Int.Ed.50: 8143 (2011)) were prepared according to the procedure reported in the literature. Bis (trimethylsiloxy) methylsilane (MD′M), (EtO) ₃ SiH and Et ₃ SiH were obtained from Momentive Performance Materials and distilled from calcium hydride prior to use. Substrates, 1-octene (TCI America), tert-butylethylene or TBE (Alfa Aesar), N, N-dimethylallylamine (TCI America) and styrene (Alfa Aesar) are dried over calcium hydride and vacuumed before use Distilled below. 1-butene (TCI America), allylamine (Alfa Aesar), and allyl isocyanate (Alfa Aesar) were dried over 4 angstrom molecular sieves. SilForce ^{(TM) SL6100 (M vi D120M vi)} , SilForce ( ^{_{TM) SL6020 (M 15 D H 30}} M), and allyl polyether is obtained from Momentive Performance Materials, 12 hours prior to use, dried under a high pressure It was.

¹ H NMR spectra were recorded operating on an Inova 400 and 500 spectrometer at 399.78 and 500.62 MHz, respectively. ¹³ C NMR spectra were recorded operating at 125.893 MHz on an Inova 500 spectrometer. All ¹ H and ¹³ C NMR chemical shifts were recorded relative to SiMe ₄ using the solvent ¹ H (residue) and ¹³ C chemical shifts as the second standard. The following abbreviations and terms were used: bs: broad singlet, s: singlet, t: triplet, bm: broad multiple, GC: Gas Chromatography, MS: Mass Spectral ), THF: tetrahydrofuran.

  GC analysis was performed on a Shimadzu GC-2010 gas chromatograph equipped with a Shimadzu AOC-20s autosampler and a Shimadzu SHRXI-5MS capillary column (15 m × 250 μm). The instrument was set to an inlet and detector temperature of 250 ° C. and 275 ° C., respectively, with an input volume of 1 μl and an inlet split ratio of 20: 1. UHP-grade helium was used as the carrier gas at a flow rate of 1.82 ml / min. The temperature program used for all analyzes was as follows: 60 ° C. for 1 minute, up to 250 ° C. at 15 ° C./minute, 2 minutes.

The loading of the catalyst described below is reported by the mol% of the cobalt complex (mol _{Co complex} / mol _olefin × 100).

Example 1: Synthesis of ( ^Mes PDI) CoN ₂ This compound was prepared by adding 0.500 g (0.948 mmol) of ( ^Mes PDI) CoCl ₂ , 0.110 g ( 4.75 g mmol, 5.05 eq ). Prepared in a similar manner to the synthesis of ( ^iPr PDI) CoN ₂ (Bowman above) using sodium and 22.0 g (108 mmol, 114 eq ) platinum. 3: 1 Recrystallization from pentene / toluene to give a very dark teal colored crystals of 0.321 ^(70%), identified as (Mes PDI) CoN _2. C ₂₇ H ₃₁ N ₅ Co Analysis: Calculated C, 66.93; H, 6.45; N, 14.45. Found C, 66.65; H, 6.88; N, 14.59. ¹ H NMR (benzene-d6): 3.58 ( 15 Hz), 4.92 (460 Hz). IR (benzene) ν _NN = 2089 cm ⁻¹ .

Example 2: Synthesis of ( ^Mes PDI) CoOH 0.100 (0.203 mmol) ( ^Mes PDI) CoCl, 0.012 g (0.30 mmol, 1.5 eq ) NaOH in a 20 ml scintillation vial and Approximately 10 ml of THL was charged. The reaction was stirred for 2 days and the color of the solution changed from dark pink to red. The THF was removed in vacuo and the residue was dissolved in approximately 20 ml of toluene. The resulting solution was filtered through Celite and the solvent was removed from the filtrate in vacuo. Recrystallization of the crude product from 3: 1 pentene / toluene yielded 0.087 g (90%) of dark pink crystals, identified as ( ^Mes PDI) CoOH. The compound was dichroic in solution and showed a greenish pink color. C ₂₇ H ₃₂ CoN ₃ O Analysis: Calculated C, 68.49; H, 6.81; N, 8.87. Found C, 68.40; H, 7.04; N, 8.77. ¹ H NMR (benzene-d ₆ ): δ = 0.26 (s, 6H, C (CH ₃ )), 1.07 (s, 1H, CoOH), 2.10 (s, 12H, o-CH _{3) ), 2.16 (s, 6H,} p-CH 3), 6.85 (s, 4H, m- aryl)), 7.49 (d, 2H , m- pyridine), 8.78 (t, 1H P-pyridine). ¹³ C { ¹ H} NMR (benzene-d ₆ ): δ = 19.13 (o-CH ₃ ), 19.42 (C (CH ₃ )), 21.20 (p-CH ₃ ), 114.74 ( p-pyridine), 121.96 (m-pyridine), 129.22 (m-aryl), 130.71 (o-aryl), 134.78 (p-aryl), 149.14 (i-aryl), 153.55 (o-pyridine), 160.78 (C = N). IR (benzene) ν _OH = 3582 cm ⁻¹ .

Example 3: Silylation of 1-octane with HD ^H M using various Co complexes In a nitrogen-filled dry box, 0.100 (0.891 mmol) 1-octene, and 0 in a scintillation vial 0.009 mmol (1 mol%) of cobalt complex (see Table 1 for specific amounts). 0.100 g (0.449 mmol, 0.50 equiv ) MD ^H M was added to the mixture and the reaction was stirred for 1 h at room temperature. The reaction was stopped by exposure to air and the product mixture was analyzed by gas chromatography and NMR spectroscopy.

Example 4: Silylation of 1-octene with different silanes using ( ^Mes PDI) CoCH ₃ and ( ^Mes PDI) CoN ₂ 0.100 g (0.891 mmol) in a scintillation vial in a dry box filled with nitrogen. ) Of 1-octene and 0.009 mmol (1 mol%) of cobalt complex (0.004 g of ( ^Mes PDI) CoCH ₃ or 0.004 g of ( ^Mes PDI) CoN ₂ ). 0.449 mmol (0.5 eq ) silane (0.100 g MD ^H M, 0.075 g (EtO) ₃ SiH or 0.052 g Et ₃ SiH) was added to the mixture and the reaction was desired For a period of time at room temperature. The reaction was stopped by exposure to air and the product mixture was analyzed by gas chromatography and NMR spectroscopy. The results are shown in Table 2.

Example 3: In Situ Activation of Cobalt Precatalyst In a 20 ml scintillation vial 0.100 g (0.891 mmol) 1-octene, 0.100 g (0.449 mmol) MD ^H M and 0.005 g ( 0.009 mmol, 1 mol%) ( ^Mes PDI) CoCl ₂ was added. 0.019 mmol (2 mol%) activator (1.0 M NaHBEt _{3 in} 0.019 ml of toluene; 0.012 ml 1.6 M CH ₃ Li in diethyl ether; 0.019 ml 1.0 M in toluene DIBAL-H; 0.003 g LiHMDS) was then added to the mixture and the reaction was stirred for 1 hour at room temperature. The reaction was stopped by exposure to air, followed by analysis of the mixture by GC. In all cases, complete conversion of 1-octene to an approximately 1: 1 mixture of 1-bis (trimethylsiloxy) methylsilyl-2-octene and octane was observed.

Example ⁴ :( Mes PDI) silylation with different silanes of Coch ₃ the use cis- and trans-4- octene.
The reaction consists of 0.100 g (0.891 mmol) cis- or trans-4-octene and 0.009 mmol (1 mol%) cobalt complex (0.004 g ( ^Mes PDI) CoCH ₃ ), and 0. Similar to 1-octene silylation using 629 mmol (0.5 eq ) silane (0.100 g MD ^H M, 0.075 g (EtO) ₃ SiH or 0.052 g Et ₃ SiH) The method was implemented. The reaction was stirred for 24 hours at room temperature, stopped by exposure to air, and analyzed by gas chromatography and NMR spectroscopy. The results are shown in Table 3.

Example 5: ( ^Mes PDI) Silylation of 1-octene with MD ^H M in the presence of H ₂ using CoCH _{3 In} a dry box filled with nitrogen, 0.200 g (1. 78 mmol) 1-octene and 0.400 g (1.80 mmol) MD ^H M were charged. The solution was frozen in a cold water reservoir and 0.008 (0.017 mmol, 1 mol%) ( ^Mes PDI) CoCH ₃ was added to the surface of the frozen solution. The reaction vessel was quickly capped, removed from the drying box, and placed in a dewar filled with liquid nitrogen to hold the frozen solution. Container is deaerated, H ₂ of approximately 1 atmosphere was placed. The solution was thawed and stirred for 1 hour. The reaction was stopped by opening the glass container towards the air. Analysis of the product mixture by GC showed over 98% conversion of 1-octene to octane (74%) and 1-bis (trimethylsiloxy) methylsilyloctane (24%).

Example 6: Hydrosilylation of 1-octane with MD ^H M using [( ^Mes PDI) CoN ₂ ] [MeB (C ₆ F ₅ ) ₃ ]
In order to generate [( ^Mes PDI) CoN ₂ ] [MeB (C ₆ F ₅ ) ₃ ], 0.004 g (0.008 mmol) of ( ^Mes PDI) CoCH ₃ , 0.005 g in a 20 ml scintillation vial ( 0.01 mmol, 1.2 eq ) B (C ₆ F ₅ ) ₃ and approximately 2 ml toluene were charged. The reaction was stirred for 10 minutes, followed by removal of the solvent in vacuo. 0.100 g (0.891 mmol) 1-octene and 0.200 g (0.899 mmol) MD ^H M were added to the vial and the reaction was stirred at room temperature for 24 hours. The reaction was stopped by exposure to air. Analysis by GC and ¹ H NMR spectroscopy showed that 1-bis (trimethylsiloxy) methylsilyloctane (68%), 1-bis (trimethylsiloxy) methylsilyl-2-octene (12%) and octane (10%) from the starting material. 90% conversion to

の分析
１−ｂｉｓ（トリメチルシロキシ）メチルシリル−２−オクテン
^１Ｈ ＮＭＲ（ベンゼン−ｄ_６）：δ＝０．１６（ｓ、３Ｈ、（ＯＴＭＳ）_２ＳｉＣＨ_３）、０．１８（ｓ、１８Ｈ、ＯＳｉ（ＣＨ_３）_３）、０．９０（ｔ、３Ｈ、Ｈ^ｈ）、１．２７（ｍ、２Ｈ、Ｈ^ｆ）、１．２９（ｍ、２Ｈ、Ｈ^ｇ）、１．４０（ｍ、２Ｈ、Ｈ^ｅ）、１．５９（ｄ、２Ｈ{７５％}、Ｈ^ａ−ｔｒａｎｓ異性体）、１．６６（ｄ、２Ｈ{２５％}、Ｈ^ａ−ｃｉｓ異性体）、２．０７（ｍ、２Ｈ{７５％}、Ｈ^ｄ−ｔｒａｎｓ異性体）、２．１１（ｍ、２Ｈ{２５％}、Ｈ^ｄ−ｃｉｓ異性体）、５．４４（ｍ、１Ｈ{７５％}、Ｈ^ｃ−ｔｒａｎｓ異性体）、５．４８（ｍ、１Ｈ{２５％}、Ｈ^ｃ−ｃｉｓ異性体）、５．５５（ｍ、１Ｈ{７５％}、Ｈ^ｂ−ｔｒａｎｓ異性体）、５．６０（ｍ、１Ｈ{２５％}、Ｈ^ｂ−ｃｉｓ異性体）。^１３Ｃ｛^１Ｈ｝ＮＭＲ（ベンゼン−ｄ_６）：δ＝−０．４６（（ＯＴＭＳ）_２ＳｉＣＨ_３）、２．０４（ＯＳｉ（ＣＨ_３）_３）、１４．３５（Ｃ^ｈ）、２２．９９（Ｃ^ｇ−ｔｒａｎｓ）、２３．０５（Ｃ^ｇ−ｃｉｓ）、２４．１２（Ｃ^ａ）、２９．８７（Ｃ^ｅ−ｃｉｓ）、３０．００（Ｃ^ｅ−ｔｒａｎｓ）、３１．７９（Ｃ^ｆ−ｔｒａｎｓ）、３２．０５（Ｃ^ｆ−ｃｉｓ）、３３．３７（Ｃ^ｄ）、１２４．３７（Ｃ^ｂ−ｃｉｓ）、１２５．１４（Ｃ^ｂ−ｔｒａｎｓ）、１２９．０６（Ｃ^ｃ−ｃｉｓ）、１３０．４７（Ｃ^ｃ−ｔｒａｎｓ）。 product:

Analysis of 1-bis (trimethylsiloxy) methylsilyl-2-octene
¹ H NMR (benzene-d ₆ ): δ = 0.16 (s, 3H, (OTMS) ₂ SiCH ₃ ), 0.18 (s, 18H, OSi (CH ₃ ) ₃ ), 0.90 (t, 3H, H ^h ), 1.27 (m, 2H, H ^f ), 1.29 (m, 2H, H ^g ), 1.40 (m, 2H, H ^e ), 1.59 (d, 2H { 75%}, H ^a -trans isomer), 1.66 (d, 2H {25%}, H ^a -cis isomer), 2.07 (m, 2H {75%}, H ^d -trans isomer) ), 2.11 (m, 2H {25%}, H ^d -cis isomer), 5.44 (m, 1H {75%}, H ^c -trans isomer), 5.48 (m, 1H { ^25%}, H c -cis isomer), 5.55 (m, 1H { 75%}, H b -trans isomer), 5.60 (m, 1H { 25%}, H b -cis isomer ). ¹³ C { ¹ H} NMR (benzene-d ₆ ): δ = −0.46 ((OTMS) ₂ SiCH ₃ ), 2.04 (OSi (CH ₃ ) ₃ ), 14.35 (C ^h ), 22 .99 (C ^g -trans), 23.05 (C ^g -cis), 24.12 (C ^a ), 29.87 (C ^e -cis), 30.00 (C ^e -trans), 31.79 (C ^f -trans), 32.05 (C ^f -cis), 33.37 (C ^d ), 124.37 (C ^b -cis), 125.14 (C ^b -trans), 129.06 (C ^{c -cis), 130.47 (C c} -trans).

1-triethoxysilyl-2-octene
¹ H NMR (benzene-d ₆ ): δ = 0.88 (t, 3H, H ^h ), 1.19 (t, 9H, OCH ₂ CH ₃ ), 1.26 (m, 2H, H ^f ), 1. ^{26 (m, 2H, H g} ), 1.36 (m2H, H e), 1.74 (d, 2H {75%}, H a -trans isomer), 1.78 (d, 2H { 25% }, H ^a -cis isomer), 2.02 (m, 2H {75%}, H ^d -trans isomer), 2.13 (m, 2H {25%}, H ^d -cis isomer), _{3.83 (q, 6H, OCH 2} CH 3), 5.45 (m, 1H {75%}, H c -trans isomer), 5.49 (m, 1H { 25%}, H c -cis Isomer), 5.66 (m, 1H {75%}, ^Hb- trans isomer), 5.69 (m, 1H {25%}, ^Hb- cis isomer). ¹³ C { ¹ H} NMR (benzene-d ₆ ): δ = 14.35 (C ^h ), 17.14 (C ^a ), 18.61 (OCH ₂ CH ₃ ), 22.98 (C ^g ), 17.14 (C ^a ), 29.87 (C ^e ), 31.72 (C ^f ), 33.26 (C ^d -trans), 33.47 (C ^d -cis), 58.69 (OCH _{2 ^{CH 3), 123.38 (C b}} -cis), 124.46 (C b -trans), 130.94 (C c -trans), 130.98 (C c -cis).

1-triethylsilyl-2-octene
¹ H NMR (benzene-d ₆ ): δ = 0.55 (t, 6H, Si (CH ₂ CH ₃ ) ₃ ), 0.91 (t, 3H, H ^h ), 0.97 (t, 9H, ^{_{Si (CH 2 CH 3) 3}} ), 1.28 (m, 2H, H f), 1.32 (m, 2H, H g), 1.36 (m, 2H, H e), 1.50 ( d, 2H {75%}, H ^a -trans isomer), 1.54 (d, 2H {25%}, H ^a -cis isomer), 2.03 (m, 2H {75%}, H ^d -Trans isomer), 2.08 (m, 2H {25%}, H ^d -cis isomer), 5.47 (m, 1H {75%}, H ^c -trans isomer), 5.50 ( m, 1H {25%}, H ^c -cis isomer), 5.36 (m, 1H {75%}, H ^b -trans isomer), 5.38 (m, 1H {25%}, H ^b -Cis difference Sex). ¹³ C { ¹ H} NMR (benzene-d ₆ ): δ = 2.82 (Si (CH ₂ CH ₃ ) ₃ ), 7.70 (Si (CH ₂ CH ₃ ) ₃ ), 14.42 (C ^h ) 17.70 (C ^a -trans), 17.71 (C ^a -cis), 23.04 (C ^g ), 23.19 (C ^e ), 29.94 (C ^f ), 32.40 (C ^d- trans), 32.47 (C ^d -cis), 126.41 (C ^b -trans), 126.46 (C ^b -cis), 129.31 (C ^c -trans), 129.33 (C ^c- cis).

Example 7: ( ^Mes PDI) Silylated thickened glass vessel with 1-butene different silane using CoCH ₃ 0.449 mmol silane (0.100 g MD′M, 0.075 g (EtO) ₃ SiH or 0.052 g Et ₃ SiH) and 0.004 g (0.009 mmol) ( ^Mes PDI) CoCH ₃ were charged. The mixture was frozen with liquid nitrogen and the reaction vessel was degassed. 0.891 mmol of 1-butene was charged to the vessel using a calibration gas valve. The mixture was thawed and stirred at room temperature for 1 hour. Volatile materials include CDCl ₃ containing J.C. Distilled into Young tubes and analyzed by NMR spectroscopy. The remaining residue was exposed to air and analyzed by GC and NMR spectroscopy. The results are shown in Table 4.

Product analysis 1-bis (trimethylsiloxy) methylsilyl-2-butene
¹ H NMR (CDCl ₃ ): δ = 0.00 and 0.01 (s, 2 × 3H, (OTMS) ₂ SiCH ₃ ), 0.08 and 0.09 (s, 2 × 18H, OSi (CH _{3 3} ), 1.38 and 1.45 (d, 2 × 2H, SiCH ₂ CH═CH), 1.57 and 1.64 (d, 2 × 3H, CH═CHCH ₃ ), 5.25 to 5 .43 (m, 4 × 1H, CH═CH). ¹³ C { ¹ H} NMR (CDCl ₃ ): δ = −0.44 and −0.60 ((OTMS) ₂ SiCH ₃ ); 1.98 (OSi (CH ₃ ) ₃ ); 18.27 (CH═ CHCH _3); 19.19 and _{23.71 (SiCH 2 CH = CH)} ; 127.17,124.12,125.34,126.09 (CH = CH).

1-triethoxysilyl-2-butene
¹ H NMR (CDCl ₃ ): δ = 1.21 (t, 2 × 9H, OCH ₂ CH ₃ ), 1.55 and 1.60 (d, 2 × 2H, SiCH ₂ CH═CH), 1.61 And 1.62 (d, 2 × 3H, CH═CHCH ₃ ), 3.81 and 3.82 (q, 2 × 6H, OCH ₂ OCH ₃ ), 5.38 and 5.48 (m, 4 × 1H) , CH = CH). ¹³ C { ¹ H} NMR (CDCl ₃ ): δ = 11.84 (SiCH ₂ CH═CH); 18.20 and 18.23 (CH═CHCH ₃ ); 18.36 and 13.38 (OCH ₂ CH _3); 58.64 and _{58.65 (OCH 2 CH 3);} 123.33,123.68,124.46,125.31 (CH = CH).

Example 8: Silylation of TBE with MD ^H M using ( ^Mes PDI) CoCH _{3 The} reaction was carried out using 0.100 g (0.449 mmol) MD ^H M, 0.004 g (0.008 mmol) ( ^Mes PDI) Performed similarly to 1-butene silylation using CoCH ₃ and 0.891 mmol TBE. Analysis of volatiles by ¹ H NMR spectroscopy showed a 4: 1 mixture of unreacted TBE and 2,2-dimethylbutane (33% conversion). Analysis of the silane product by GC and NMR spectroscopy showed only trans-1-bis (trimethylsiloxy) methylsilyl-3,3-dimethyl-1-butene.
¹ H NMR (CDCl ₃ ): δ = 0.00 (s, 3H, (OTMS) ₂ SiCH ₃ ), 0.09 (s, 18H, OSi (CH ₃ ) ₃ ), 0.99 (s, 9H, OSi (CH ₃ ) ₃ ), 5.37 (d, J = 19.07, 1H SiCH═CH), 6.13 (d, J = 19.07 Hz , 1H, CH═CHC (CH ₃ ) ₃ ) . ¹³ C { ¹ H} NMR (CDCl ₃ ): δ = 0.00 ((OTMS) ₂ SiCH ₃ ); 2.01 (OSi (CH ₃ ) ₃ ); 28.96 (C (CH ₃ ) ₃ )) 34.91 (C (CH ₃ ) ₃ )); 121.01 (SiCH═CH); 159.23 (SiCH═CH).

Example 9: 0.090 g (1.1 mmol) in a scintillation vial in a silylated nitrogen-filled dry box with different silanes of N, N-dimethylallylamine using ( ^Mes PDI) CoCH ₃ and ( ^Mes PDI) CoN ₂ ) N, N-dimethylallylamine and 0.50 mmol (0.5 eq ) silane (0.118 g MD ^H M, 0.087 g (EtO) ₃ SiH or 0.062 g Et ₃ SiH) Filled. 0.01 mmol (0.1 mol%) cobalt complex (0.005 g ( ^Mes PDI) CoCH ₃ or 0.005 g ( ^Mes PDI) CoN ₂ ) was added and the reaction was stirred at room temperature for 1 hour. . The reaction was stopped by exposure to air and the product mixture was analyzed by NMR spectroscopy. The results are shown in Table 5.

Analysis of product N, N-dimethyl-3-bis (trimethylsiloxy) methylsilyl-1-propenylamine
¹ H NMR (benzene-d ₆ ): δ = 0.14 (s, 3H, (OTMS) ₂ SiCH ₃ ), 0.18 (s, 18H, OSi (CH ₃ ) ₃ ), 1.50 (dd, J = 7.7, 1.2 Hz, 2H, SiCH ₂ CH═CH), 2.35 (s, 6H, N (CH ₃ ) ₂ ), 4.25 (dt, J = 13.6, 7.7 Hz) _{, 1H, CH 2 CH = CH} ), 5.80 (dt, J = 13.6,1.2Hz, 1H, CH 2 CH = CH). ¹³ C { ¹ H} NMR (benzene-d ₆ ): δ = 0.61 ((OTMS) ₂ SiCH ₃ ); 2.12 (OSi (CH ₃ ) ₃ )); 20.49 (SiCH ₂ CH═CH ), 41.08 (N (CH ₃ ) ₂ ), 94.09 (CH ₂ CH═CH), 140.57 (CH ₂ CH═CH).

N, N-dimethyl-3-triethoxysilyl-1-propenylamine
¹ H NMR (benzene-d ₆ ): δ = 1.18 (t, J = 7.0, 9H, OCH ₂ CH ₃ ), 1.66 (dd, J = 7.5, 1.2 Hz, 2H, SiCH ₂ CH═CH), 2.30 (s, 6H, N (CH ₃ ) ₂ ), 3.84 (q, J = 7.0, 6H, OCH ₂ CH ₃ ), 4.31 (dt, J _{= 13.6,7.5Hz, 1H, CH 2 CH} = CH), 5.85 (dt, J = 13.6,1.2Hz, 1H, CH 2 CH = CH). ¹³ C { ¹ H} NMR (benzene-d ₆ ): 13.48 (SiCH ₂ CH═CH), 18.41 (OCH ₂ CH ₃ ), 40.98 (N (CH ₃ ) ₂ ), 58.65 _{(OCH 2 CH 3), 92.95} (CH 2 CH = CH), 140.82 (CH 2 CH = CH).

Example 10: Silylation of methyl-capped allyl polyether (H ₂ C═CHCH ₂ O (C ₂ H ₄ O) _8.9 CH ₃ ) with methyl bis (trimethylsiloxy) silane (MD ^H M) Scintillation vial Of 0.100 g of the average formula H ₂ C═CHCH ₂ O (C ₂ H ₄ O) _8.9 CH ₃ methyl-capped allyl polyether and 0.025 g (0.11 mmol, 0.5 eq ) MD'M was filled. To the stirring solution of polyether and silane was added 1 mg (0.002 mmol; 1 mol%) of ( ^Mes PDI) CoCH ₃ . The scintillation vial was sealed, removed from the drying box and placed in an oil bath at 65 ° C. The reaction mixture was stirred for 1 hour, the vial was removed from the oil bath and the reaction was stopped by opening the container to air. ¹ H HMR spectroscopy of the product demonstrated a 1: 1 mixture of silylated product and propyl polyether.

_{(OTMS) 2 Si (CH 3} ) CH 2 CH = CHO (C 2 H 4 O) 8.9 CH 3
¹ H NMR (CDCl ₃ ): δ = −0.06 (s, 3H, (OTMS) ₂ SiCH ₃ ), 0.03 (s, 18H, OSi (CH ₃ ) ₃ ), 1.55 (dd, J _{= 7.8,1.1Hz, 2H, SiCH 2 CH} = CH), 3.32 (s, 3H, OCH 3), 3.5-3.7 (OCH 2 CH 2 -O), 5. _{28 (dt, J = 18.5,1.1Hz,} 1H, CH 2 CH = CH), 6.07 (dt, J = 18.5,7.8Hz, 1H, CH 2 CH = CH). ¹³ C { ¹ H} NMR (CDCl ₃ ): δ = 0.11 ((OTMS) ₂ SiCH ₃ ), 1.65 (OSi (CH ₃ ) ₃ ), 29.24 (SiCH ₂ CH═CH); 59 _{.0 (OCH 3), 70-72 (} OCH 2 CH 2 -O), 127.02 (CH 2 CH = CH), 144.38 (CH 2 CH = CH).

Example 11 Hydrosilylated Styrene In a thick glass container, 0.500 g (4.80 mmol) styrene, 1.080 g (4.854 mmol, 1.01 eq ) MD′M and 0.020 g (0.005 mmol). 042 mmol, 1 mol%) ( ^Mes PDI) CoCH ₃ was charged. The reaction was stirred for 96 hours at 75 ° C. in an oil bath and stopped by exposure to air. Analysis of the product mixture by ¹ H NMR spectroscopy showed 20% conversion of styrene to Bis (trimethylsiloxy) methyl (phenylethyl) silane (15%) and ethylbenzene (5%). Bis (trimethylsiloxy) methyl (phenylethyl) silane, [(OTMS) ₂ SiCH ₃ ] ₂ was observed by GC / MS.

Example 12: Cross-linking of M ^vi D ₁₂₀ M ^vi (SL6100) and MD ₁₅ ^DH ₃₀ M (SL6020) at room temperature 1.0 g M ^vi D ₁₂₀ M ^vi (SL6100) in a scintillation vial where M ^vi is VinyldimethylSiO ) and 0.044 g MD ₁₅ ^DH ₃₀ M (SL6020) were charged. In the second vial, a solution of the catalyst was prepared by dissolving 0.010 grams of ( ^Mes PDI) CoCH ₃ or ( ^Mes PDI) CoN ₂ in approximately 0.300 g of toluene. The catalyst solution was added to the stirring solution of SL6100 and SL6020 and the reaction was observed in gel formation. The gel produced after the reaction was stopped by exposure to air was softer than that obtained by the same reaction using Karstedt's compound as a catalyst.

Polymer cross-linking in stock solution conditions was also examined by adding 0.010 g ( ^Mes PDI) CoCH ₃ or ( ^Mes PDI) CoN ₂ to a stirring solution of 1.0 g SL6100 and 0.044 g SL6020. It was. A soft gel was again obtained from these reactions.

Example 13: Cross-linking of M ^vi D ₁₂₀ M ^vi (SL6100) and MD ₁₅ ^DH ₃₀ M (SL6020) at 65 ° C. These reactions were removed from the drying box after sealing a scintillation vial and an oil at 65 ° C. Performed in a manner similar to that performed at room temperature, including the additional step of placing in the bath. The gel produced after stopping the reaction was indistinguishable from that obtained by the same reaction using Karstedt's compound as a catalyst. The results are shown in Table 6.

Double Silylation Experiment Example 14: Silylation of 1-bis (trimethylsiloxy) methylsilyl-2-octene with MD ^H M using ( ^Mes PDI) CoCH ₃ This experiment was performed with 0.100 g (0.301 mmol) 1-bis (trimethylsiloxy) methylsilyl-2-octene, 0.034 g (0.152 mmol, 0.51 eq ) MD′M and 0.001 g (0.002 mmol, 1 mol%) ( ^Mes PDI) ) Performed in a manner similar to 1-octene silylation using CoCH ₃ . The reaction was stirred at room temperature for 24 hours and stopped by exposure to air. Analysis of the mixture by GC-FID, GC-MS and NMR spectroscopy was performed using 1-bis (trimethylsiloxy) methylsilyloctane and 1,8-bis (bis (trimethylsiloxy) methylsilyl) -2-octene (most isomers). Body) approximately 1: 1 mixture.

Attempts to silylate 1-trimethoxysilyl-2-octene with MD ^H M resulted in a mixture of disilylation products with the formation of 1-triethoxysilyloctane. The silylation of 1-bis (trimethylsiloxy) methylsilyl-2-octene and 1-triethoxysilyl-2-octene with TES under the same conditions was carried out by 1-bis (trimethylsiloxy) methylsilyloctane and 1-trimethyl respectively. Only the hydrogenated product of ethoxysilyloctane resulted.

Example 15: Alternative procedure for double silylation of 1-octene with MD ^H M using ( ^Mes PDI) CoCH ₃ This experiment consists of 0.100 g (0.891 mmol) of 1-octene, Silylation of 1-octene using 0.150 g (0.674 mmol, 0.756 eq ) MD ^H M and 0.004 g (0.008 mmol, 1 mol%) ( ^Mes PDI) CoCH ₃ Was carried out in a similar manner. The reaction was stirred at room temperature for 24 hours and stopped by exposure to air. GC-FID analysis of the mixture revealed that approximately 1 of octane, 1-bis (trimethylsiloxy) methylsilyloctane and 1,8-bis (bis (trimethylsiloxy) methylsilyl) -2-octene (most isomers), respectively. : 0.5: 0.5 mixture was shown.

Example 16: ( ^Mes PDI) Silylation of 1-bis (trimethylsiloxy) methylsilyl-2-butene with MD ^H M using CoCH ₃ This experiment was performed using 0.100 g (0.361 mmol) of 1-bis ( Trimethylsiloxy) methylsilyl-2-butene, 0.040 g (0.18 mmol, 0.50 equiv ) MD ^H M and 0.002 g (0.004 mmol, 1 mol%) ( ^Mes PDI) CoCH ₃ And was performed in a manner similar to the silylation of 1-bis (trimethylsiloxy) methylsilyl-2-octene. The reaction was stirred for 24 hours and stopped by exposure to air. Analysis of the mixture by NMR spectroscopy showed the following product distribution: 50% 1-bis (trimethylsiloxy) methylsilylbutane, 26% trans-1,4-bis (bis (trimethylsiloxy) methylsilyl) 2-butene, 17% cis-1,4-bis (bis (trimethylsiloxy) methylsilyl) -2-butene, 5% trans-1,3-bis (bis (trimethylsiloxy) methylsilyl) -1-butene , And 2% trans-1,4-bis (bis (trimethylsiloxy) methylsilyl) -1-butene.

Product analysis 1-bis (trimethylsiloxy) methylsilylbutane
¹ H NMR (CDCl ₃ ): δ = 0.01 (s, 3H, (OTMS) ₂ SiCH ₃ ), 0.09 (s, 18H, OSi (CH ₃ ) ₃ ), 0.45 (m, 2H, _{SiCH 2 CH 2 CH 2 CH 3} ), 0.88 (t, 3H, SiCH 2 CH 2 CH 2 CH 3), 1.26-1.33 (m, 4H, SiCH 2 CH 2 CH 2 CH 3). ¹³ C { ¹ H} NMR (CDCl ₃ ): δ = −0.66 (OTMS) ₂ SiCH ₃ ), 2.02 (OSi (CH ₃ ) ₃ ), 13.98 (SiCH ₂ CH ₂ CH ₂ CH _{3 ), 17.46 (SiCH 2 CH 2} CH 2 CH 3), 25.35 and _{26.36 (SiCH 2 CH 2 CH 2} CH 3).

Trans-1,4-bis (bis (trimethylsiloxy) methylsilyl) -2-butene
¹ H NMR (CDCl ₃ ): δ = 0.01 (s, 3H, (OTMS) ₂ SiCH ₃ ), 0.09 (s, 18H, OSi (CH ₃ ) ₃ ), 1.39 (d, 4H, _{SiCH 2 CH = CHCH 2 Si)} , 5.21 (t, 2H, SiCH 2 CH = CHCH 2 Si). ¹³ C { ¹ H} NMR (CDCl ₃ ): δ = −0.66 ((OTMS) ₂ SiCH ₃ ), 2.02 (OSi (CH ₃ ) ₃ ), 23.95 (SiCH ₂ CH═CHCH ₂ Si) ), 124.28 (SiCH ₂ CH═CHCH ₂ Si).

Cis-1,4-bis (bis (trimethylsiloxy) methylsilyl) -2-butene
¹ H NMR (CDCl ₃ ): δ = 0.01 (s, 3H, (OTMS) ₂ SiCH ₃ ), 0.09 (s, 18H, OSi (CH ₃ ) ₃ ), 1.41 (d, 4H, _{SiCH 2 CH = CHCH 2 Si)} , 5.31 (t, 2H, SiCH 2 CH = CHCH 2 Si). ¹³ C { ¹ H} NMR (CDCl ₃ ): δ = −0.38 ((OTMS) ₂ SiCH ₃ ), 2.01 (OSi (CH ₃ ) ₃ ), 19.12 (SiCH ₂ CH═CHCH ₂ Si) ), 122.86 (SiCH ₂ CH═CHCH ₂ Si).

Trans-1,3-bis (bis (trimethylsiloxy) methylsilyl) -1-butene
¹ H NMR (CDCl ₃ ): δ = 0.01 (s, 3H, (OTMS) ₂ SiCH ₃ ), 0.09 (s, 18H, OSi (CH ₃ ) ₃ ), 1.04 (d, 3H, _{CHCH 3), 1.64 (m,} 1H, CHCH 3), 5.28 (d, 1H, SiCH = CH), 6.27 (dd, 1H, SiCH = CH). ¹³ C { ¹ H} NMR (CDCl ₃ ): δ = −0.13 ((OTMS) ₂ SiCH ₃ ), 2.00 (OSi (CH ₃ ) ₃ ), 12.07 (CHCH ₃ ), 31.69 _{(CHCH 3), 123.37 (SiCH} = CH), 151.01 (SiCH = CH).

Trans- 1,4-bis (bis (trimethylsiloxy) methylsilyl) -1-butene
¹ H NMR (CDCl ₃ ): δ = 0.01 (s, 3H, (OTMS) ₂ SiCH ₃ ), 0.09 (s, 18H, OSi (CH ₃ ) ₃ ), 0.58 (m, 2H, CH ₂ CH ₂ Si), 2.11 (m, 2H, CH ₂ CH ₂ Si), 5.46 (d, 1H, SiCH═CH), 6.20 (m, 1H, SiCH═CH), ¹³ C { ¹ H} NMR (CDCl ₃ ): δ = 0.29 ((OTMS) ₂ SiCH ₃ ), 2.07 (OSi (CH ₃ ) ₃ ), 16.28 (CH ₂ CH ₂ Si), 29.79 _{(CH 2 CH 2 Si),} 125.73 (SiCH = CH), 151.52 (SiCH = CH).

Examples 17A-17F: Crosslinking of Polysiloxane with Olefin Using ( ^Mes PDI) CoCH ₃ 0.002 g (0.004 mmol, 2000 ppm catalyst loaded) of ( ^Mes PDI) CoCH ₃ and olefin (specific) For the correct amount) (see Table 7). The mixture was stirred until a uniform pink solution was obtained. Typically this step required stirring for 5-20 minutes. Polysiloxane (1: 0.75 C = C to Si—H ratio, Table 7) was added to the reaction vessel and the mixture was stirred in an oil bath at 65 ° C. for 4-6 hours. The resulting gel was ground into a powder using a mortar and pestle, washed with hexane to remove alkane by-products, and dried in vacuo overnight.

Each of the hexane-extracted samples was analyzed with a Bruker AVANCE 400WB spectrometer using nuclear magnetic resonance (NMR) spectroscopy, with a field strength of 9.40 T and ¹ H resonance of 400 MHz. A single pulse excitation (SPE) pulse arrangement with magic angle spinning (MAS) is used, the { ¹ H- ¹³ C} SPE / MAS NMR spectrum has a 150 second delay, and the { ¹ H- ²⁹ Si} SPE There was a 300 second delay in the / MAS NMR spectrum. A cross-polarized (CP) pulse sequence by magic angle spinning (MAS) was used for the { ¹ H- ¹³ C} CP / MAS NMR spectrum with a 10 second delay and a 5 ms contact time. About 0.1 g of each sample is packed into a 4 mm zirconia (ZrO ₂ ) rotor with a Kel-F cap, the rotor spin is ˜8 to 10.8 kHz for ²⁹ Si, and ¹³ C for It was 10.8 kHz. The number of co-addition scans was 1000 ( ¹³ C) or 512 ( ²⁹ Si) for SPE data and 16,000 for CP / MAS ¹³ C data. The processing parameters used were zero fixed to 4x, 5 or 15 Hz LB for ¹³ C data, and 30 Hz for ²⁹ Si data.

Results of ¹³ C NMR Olefin: 1-octene The chemical shifts of the samples of Examples 17A, 17C and 17E and their ¹³ C SPE / MAS and CP / MAS NMR spectral assignments are summarized in Table 8. The spectra show three different chemical shifts: δ2 to δ-2 consistent with methyl on silicon (CH ₃ Si), δ14-35 consistent with linear hydrocarbons, and δ124-135 with olefin (sp ² ) carbon. Multiple signals in the region were shown. The absence of a signal at ~ δ115 indicates that there is no residue of unreacted 1-octene. Data from two different experiments show significant differences. Significant loss in the region of CH _2, CH ₃ and olefinic carbon is observed. Result, while more mobile phase sample is a hydrocarbon of saturated and unsaturated, from a more rigid phase following structure _{≡SiCH 2 CH 2 CH 2 (CH} 2) 2 CH 2 CH 2 CH 2 Si≡ I showed that. However, in the CP experiment, the olefin signal was mostly present. This result indicates the presence of an unsaturated structure ≡SiCH ₂ CH ₂ CH═CH (CH ₂ ) ₂ CH ₂ CH ₂ CH ₃ with an internal double bond (a double bond can be present in the 2-6 position) Note).

The two signals due to olefinic carbon found at δ125 and δ131 were found to be approximately the same intensity. This signal is consistent with double bonds at the 2 and 6 positions. The CP data for sample 17A shows a very weak peak observed at δ14, indicating that most structures are trans when the double bond is in the 6 position. The methyl group —CH═CHCH ₃ at the trans 6 position overlaps with the signal seen at δ18. The weak signal near δ130 is consistent with a double bond at the 3, 4 or 5 position.

2. Olefin: 1-octadecene The chemical shifts of the samples of Examples 17B, 17D and 17F and their ¹³ C SPE / MAS and CP / MAS NMR spectral assignments are summarized in Table 9. The spectrum is very similar to the 1-octene cross-linked sample, δ2 to δ-2 consistent with methyl on silicon (CH ₃ Si), δ14-35 consistent with linear hydrocarbons and olefins (sp ² ) Multiple signals in three different chemical shift regions from δ124 to 135 by carbon were shown. However, the signal seen at ~ δ30 was significantly stronger due to the larger number of 1-octadecene starting methylene groups (CH ₂ ). The second difference was found in the olefin chemical shift range. The peak seen at ~ δ125 was not the same as the peak seen at ~ δ131. This suggests that the double bond is internal rather than near one of the ends.

The following list summarizes similarities to the 1-octene data results.
-A peak is not seen in -delta115, and it shows that there is no residue of unreacted 1-octadecene.
· SPE and CP _data, indicating that the significantly lost in the peak region of the CH 2, CH ₃ and olefinic carbon.
· More mobile phase samples while a hydrocarbon of saturated and unsaturated, harder phase consists of the following structural _{≡SiCH 2 CH 2 CH 2 (CH} 2) 1 2 CH 2 CH 2 CH 2 Si≡ .
CP experiments showed most olefin signals showing the following types of structures: ≡SiCH ₂ CH ₂ CH═CH (CH ₂ ) ₁₂ CH ₂ CH ₂ CH ₃ (note that a double bond may be present at positions 2-16). The disappearance of the CH ₃ peak near δ 15 seen in the CP / MAS experiment is the methyl group associated with the hydrocarbon-type molecule in the mobile phase and the structure of the following type ≡SiCH ₂ CH ₂ CH═CH (CH ₂ ) ₁₃ CH _This is due to the combination of ₃ and the disappearance strength is due to the groups present at the molecular ends, resulting in greater mobility. The methyl group is also from the cross-linking point.

The chemical shifts and assignments of 29Si SPE / MAS NMR spectra of the six samples of Example 17 are summarized in Table 10. The signal observed at δ - 26 is attributed to D ^* , ≡SiCH ₂ CH═CHCH ₂ (CH ₂ ) _x CH ₃ having an allyl or organofunctional group having a double bond at two positions. This signal was very strong in Example 17A compared to the spectra of the other samples. There is also a slight tendency for the peaks to be slightly wider when the sample is prepared with 1-octene than with 1-octadecene. This signal integration was grouped with the stronger signal seen at δ-22 because the peaks overlap most of the sample.

The spectra of the two samples (Examples 17A and 17B) prepared by the SiH fluid, MD ₃₀ ^DH ₁₅ M, show many that are a combination of cyclic D ₃ and D ¹ type species, at δ-35 Contains no signal.

  For the rheological properties of the product, different moduli arising from the molecule are expected based on the crosslink density and the chain length of the crosslinked molecule.

Examples 18A-18B
These examples show deuterium labeling experiments performed to demonstrate the occurrence of dehydrogenated hydrosilylation when the reaction of hydrosiloxane and olefin is catalyzed by ( ^Mes PDI) CoCH ₃ .

Example 18A: Silylation of 1-octene with (OTMS) ₂ CH ₃ Si-D (MD ^H M-d ₁ ) This reaction was reacted with 0.050 g (0.45 mmol) of 1-octene, 0.050 g (0.22 mmol, 0.5 eq ) MD ^H M-d ₁ (70% deuterated), and 0.002 g (0.004 mmol, 1 mol%) ( ^Mes PDI) CoCH ₃ This was carried out in the same manner as the silylation of 1-octene with MD ^H M. After stirring for 1 hour at room temperature, the reaction was stopped. The ² H NMR spectrum of the product mixture shows deuterium incorporation on both the methyl and methylene groups of octane and the deuterium on C ^b , C ^c and C ^d on 1-bis (trimethylsiloxy) methylsilyl-2-octene. A trace of hydrogen was shown.

Example 18B: Deuteration of 1-bis (trimethylsiloxy) methylsilyl-2-octene In a dry box filled with nitrogen, In a Young tube 0.080 g (0.24 mmol) 1-bis (trimethylsiloxy) methylsilyl-2-octene, 0.005 g (0.011 mmol, 4 mol%) ( ^Mes PDI) CoCH ₃ , and approximately 0 . 7 ml of benzene-d ₆ was charged. Tube is degassed, D ₂ of approximately 1 atmosphere was placed. The solution was thawed to room temperature and placed in an oil bath at 45 ° C. for 16 hours. Analysis of the ¹ H and ² H NMR spectra of the product mixture showed from partial deuteration of the starting material to a product fully saturated with deuterium that collects all along the octyl chains of both compounds. Deuteration basically occurs at the C2 and C3 positions, indicating that the unsaturation of the starting material is primarily allyl and not vinyl.

Examples 19A-19D: Olefin Isomerization Experiment Example 19A shows that ( ^Mes PDI) CoCH ₃ does not isomerize 1-octene.
A scintillation vial was charged with 0.100 g (0.891 mmol) of 1-octene and 0.004 g (0.008 mmol, 1 mol%) of ( ^Mes PDI) CoCH ₃ . The solution was stirred at room temperature for 1 hour and quenched by exposure to air. The ¹ H NMR spectrum of the product showed only 1-octene and traces of free ligand and no olefin isomerization.

Example 19B shows that 1-octene isomerization is not observed by ( ^Mes PDI) CoCH ₃ and the hydridotrisiloxane MD ^H M is trace.
The experiment showed that 0.100 g (0.891 mmol) 1-octene and 0.004 g (0.008 mmol, 1 mol%) ( ^Mes PDI) CoCH ₃ and 0. Performed similarly to the experiment described in Example 19A above, using 0 14 g (0.063, 7 mol%) MD ^H M. ¹ H NMR spectrum of the product showed only 1-octene, shows the free ligand and 1-bis (trimethylsiloxy) methylsilyl-2-octene traces, OH olefin isomerization was not shown.

Example 19C ^illustrates the (Mes PDI) CoCH ₃ to use N, N-dimethyl allylamine _{(CH 3) 2 NCH 2 CH} = isomerization of CH _2.
J. et al. In a Young tube 0.017 g (0.20 mmol) N, N-dimethylallylamine, 0.002 g (0.004 mmol, 2 mol%) ( ^Mes PDI) CoCH ₃ and approximately 0.7 ml benzene-d ₆ Filled. The solution was placed at room temperature and observed with ¹ H NMR spectroscopy. The isomerization of the starting material to N, N- dimethyl-1- propenylamine , (CH ₃ ) ₂ NCH═CHCH ₃ was 20% complete after 8 hours and 65% complete after 46 hours.

Example 19D ^shows (Mes PDI) CoCH ₃ to use N, N-dimethyl allylamine _{(CH 3) 2 NCH 2 CH} = hydrido trisiloxane MD isomerization and a small amount of CH ₂ ^H M.
The reaction was performed by reacting 0.091 g (1.1 mmol) N, N-dimethylallylamine, 0.003 g (0.006 mmol, 0.6 mol%) ( ^Mes PDI) CoCH ₃ , and 0.006 g (0 .03 mmol, were carried out as experiments described in example 19 C described above using the MD ^H M of 3 mol%). N from starting materials, N- dimethyl-1-propenyl _{amine, (CH} 3) isomerization of 2 NC H = CHCH ₃ is 90% complete after 8 hours and was complete after 24 hours> 95%.

EXAMPLE 20A-2 0 C: Silylation of propylene with different silanes using ( ^Mes PDI) CoCH ₃ This reaction was performed using 0.11 mmol of silane (0.025 g MD ^H M, 0.018 g (EtO) _3. SiH or 0.015 g (OEt) ₂ CH ₃ SiH), 0.001 g (0.002 mmol) ( ^Mes PDI) CoCH ₃ and 5.6 mmol (50 eq ) propylene . Performed similarly to silylation . Non-volatile materials were analyzed by NMR spectroscopy.

Analysis of the product of Example 20A 3-bis (trimethylsiloxy) methylsilyl-1-propene
¹ H NMR (CDCl ₃ ): δ = 0.03 (s, 3H, (OTMS) ₂ SiCH ₃ ), 0.09 (s, 18H, OSi (CH ₃ ) 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 = 15Hz, _{1H, CH 2 CH = C (} H) H), 5.77 (m, 1H, CH 2 CH = CH 2). ¹³ C { ¹ H} NMR (CDCl ₃ ): δ = −0.77 ((OTMS) ₂ SiCH ₃ ), 1.97 (OSi (CH ₃ ) ₃ ), 25.82 (SiCH ₂ CH═CH), _{113.72 (CH 2 CH = CH 2} ), 134.28 (CH 2 CH = CH 2).

1-bis (trimethylsiloxy) methylsilylpropane
¹ H NMR (CDCl ₃ ): δ = 0.00 (s, 3H, (OTMS) ₂ SiCH ₃ ), 0.09 (s, 18H, OSi (CH ₃ ) ₃ ), 0.46 (m, 2H, _{SiCH 2 CH 2 CH 3),} 0.95 (t, 3H, SiCH 2 CH 2 CH 3), 1.36 (m, 2H, SiCH 2 CH 2 CH 3). ¹³ C { ¹ H} NMR (CDCl 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).

Analysis of the product of Example 20B 3-Triethoxysilyl-1-propene
¹ H NMR (CDCl ₃ ): δ = 1.22 (t, 9H, OCH ₂ CH ₃ ), 1.67 (d, 2H, SiCH ₂ CH═CH), 3.84 (q, 6H, OCH ₂ HC) _{3), 4.90- 5.05 (d,} 2H, CH 2 CH = CH 2), 5.81 (m, 1H, CH 2 CH = CH 2). ¹³ C { ¹ H} NMR (CDCl ₃ ): δ = 18.36 (OCH ₂ CH ₃ ), 19.34 (SiCH ₂ CH═CH), 58. 73 (OCH ₂ HC ₃ ), 114.85 (CH ₂ CH═CH ₂ ), 132.80 (CH ₂ CH═CH ₂ ).

1-triethoxysilylpropane
¹ H NMR (CDCl ₃ ): δ = 0.63 (m, 2H, SiCH ₂ CH ₂ CH ₃ ), 0.97 (t, 3H, SiCH ₂ CH ₂ CH ₃ ), 1.22 (t, 9H, _{OCH 2 CH 3), 1.45 (} m, 2H, SiCH 2 CH 2 CH 3). ¹³ C { ¹ H} NMR (CDCl 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).

Analysis of the product of Example 20C
3-Diethoxymethylsilyl-1-propene
¹ H NMR (CDCl ₃ ): δ = 0.11 (s, 3H, SiCH ₃ ), 1.19 (t, 6H, OCH ₂ CH ₃ ), 1.63 (d, 2H, SiCH ₂ CH═C H _{), 3.76 (q, 4H,} OCH 2 CH 3), 4.88 (d, 1H, CH 2 CH = C (H) H), 4.93 (d, 1H, CH 2 CH = C (H _{) H), 5.80 (m,} 1H, CH 2 CH = CH 2). ¹³ C { ¹ H} NMR (CDCl ₃ ): δ = −5.19 (SiCH ₃ ), 18.44 (OCH ₂ CH ₃ ), 21.92 (SiCH ₂ CH═CH ) , 58.41 (OCH _{2 CH 3), 114.5 (CH} 2 CH = CH 2), 133.36 (CH 2 CH = CH 2).

1-diethoxymethylsilylpropane
¹ H NMR (CDCl ₃ ): δ = 0.08 (s, 3H, SiCH ₃ ), 0.59 (m, 2H, SiCH ₂ CH ₂ CH ₃ ), 0.94 (t, 3H, SiCH ₂ CH _{2 CH 3), 1.19 (t,} 9H, OCH 2 CH 3), 1.38 (m, 2H, SiCH 2 CH 2 CH 3). ¹³ C { ¹ H} NMR (CDCl 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).

The foregoing description includes many specific examples, which are not meant to limit the scope of the invention, but merely illustrate preferred embodiments thereof. Those skilled in the art will envision many other modifications without departing from the scope and spirit of the invention as defined in the claims appended hereto.

Claims (36)

A process for producing a dehydrogenated silylation product comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silyl hydride functional group, and ( c) comprising reacting the mixture containing the catalyst, optionally in the presence of a solvent, to produce a dehydrogenated silylation product, wherein the catalyst is of formula (I):

Complex or adduct thereof,
Where
Each 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 fluoro, chloro, bromo, iodo and -OR ³⁰ [R ³⁰ is an inert functional group selected from ethers of hydrocarbyl or substituted hydrocarbyl] , wherein R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated Forming a ring,
L is hydroxyl or C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, or component (a), wherein L optionally contains at least one heteroatom.
process.   The process of claim 1 wherein the dehydrogenated silylation product contains a silane or siloxane containing silyl and unsaturated groups. The process according to claim 1 or 2 , wherein the molar ratio of unsaturated groups in component (a) to silylhydride functional groups in component (b) is 1: 1 or less. The process according to claim 1 or 2 , wherein the molar ratio of unsaturated groups in component (a) to silylhydride functional groups in component (b) is greater than 1: 1. The process according to any one of claims 1 to 4 , wherein component (a) is a monounsaturated compound. Component (a) is an olefin, cycloalkene, alkyl-capped allyl polyether, vinyl functionalized alkyl-capped allyl or methallyl polyether, alkyl-capped terminally unsaturated amine, alkyne, terminally unsaturated acrylate or methacrylate, unsaturated arylether , vinyl functionalized polymer or oligomer, vinyl functional silanes, vinyl functional silicones, unsaturated fatty acids, unsaturated esters, as well as selected from the group consisting a combination thereof, according to any one of claims 1-4 Process. The component (a) is N, N-dimethylallylamine, allyloxy substituted polyether, propylene, cyclohexene, linear alpha olefin, internal olefin, branched olefin, unsaturated polyolefin, vinyl siloxane of formula (VIII) and combinations thereof Wherein formula (VIII) is selected from the group consisting of:

And
Wherein the alkyl of each ^{R 8} is independently C1 - C18, a substituted alkyl, vinyl, aryl or substituted aryl, of C1 - C18, n is equal to 0 or greater than or 0, according to claim 6 Process. The component (b) is R _a SiH _4-a , (RO) _a SiH _4-a , HSiR _a (OR) _3-a , R ₃ Si (CH ₂ ) _f (SiR ₂ O) _k SiR ₂ H, _{(RO) 3 Si (CH 2} ) f (SiR 2 O) k SiR 2 H, Q u T v T H p D w D H x M H y M z and is selected from the group consisting of,
Wherein, Q is _{SiO 4/2,} T is R'SiO _3/2, ^{T H} is _{HSiO 3/2,} D is R 'is ₂ SiO _2/2, ^{D H} is R' is HSiO _2/2, ^{M H} is' a _{3-g SiO 1/2,} M is R _{'H g} R a ₃ SiO _1/2, each R and R' are the C1~C18 independently Alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R and R ′ optionally contain at least one heteroatom, each of a independently has a value of 1 to 3, f has a value from 1 to 8, k has a value from 1 to 11, g has a value from 1 to 3, p is from 0 to 20, u is from 0 to 20, v is from 0 20, w is 0 to 1000, x is 0 to 1000, y is 0 to 20, and z is 0 The process according to any one of claims 1 to 7, wherein the process is such that p + x + y is equal to 1 to 3000, and the valences of all elements in the silylhydride are satisfied.   9. The process of claim 8, wherein p, u, v, y and z are 0 to 10 and w and x are 0 to 100, where p + x + y is equal to 1 to 100. The process according to any one of claims 1 to 7, wherein the component (b) has one of the following structures.
R ¹ _a (R ² O) _b SiH (Formula IX)

Where
Each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, R ⁶ is hydrogen, C1-C18 Alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, x and w are independently greater than or equal to 0 (in formula X, x is at least equal to 1), and a and b are from 0 The condition is an integer of 3 and a + b = 3. The catalyst according to claim 1, wherein the catalyst is a salt of MeB (C ₆ F ₅ ) ₃ ^— or [B [3,5- (CF ₃ ) ₂ C ₆ H ₃ ] ₄ ] — of the complex of formula (I) . A process according to any one of the preceding claims. At least one of R ⁶ and R ⁷ is

And
Where
Each of R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or fluoro, chloro, bromo, iodo and An inert functional group selected from ethers of —OR ³⁰ [R ³⁰ is hydrocarbyl or substituted hydrocarbyl] , wherein R ^{8 to} R ¹² other than hydrogen optionally contain at least one heteroatom. The process according to any one of 1 to 11 . Complex is fixed on a support, the support is selected from carbon, silica, alumina, MgCl _2, zirconia, polyethylene, polypropylene, polystyrene, poly (aminostyrene), sulfonated polystyrene, from dendrimers and a combination thereof The process according to any one of claims 1 to 12, wherein: The catalyst comprises a liquid precursor containing at least one component selected from the group consisting of a catalyst precursor and an activator , a solvent, a silyl hydride, a compound containing at least one unsaturated group, and combinations thereof. Can be produced in situ by contacting in the presence, wherein the catalyst precursor is of the structural formula (IV)

Represented by
Where
Each 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 fluoro, chloro, bromo, iodo and -OR ³⁰ [R ³⁰ is an inert functional group selected from ethers of hydrocarbyl or substituted hydrocarbyl] , wherein R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated Forming a ring structure,
X ^{is, F -, Cl -, Br} -, I -, CF 3 R 40 SO 3 - or ^R 50 COO ^- is selected from the group consisting of ^{wherein, R 40} is an alkylene group covalently or C1~C6 And R ⁵⁰ is a C1-C10 hydrocarbyl group;
The activator is a reducing agent or an alkylating agent selected from the group consisting of NaHBEt ₃ , CH ₃ Li, DIBAL-H, LiHMDS, and combinations thereof, according to any one of claims 1 to 13. The process described. The process according to any one of claims 1 to 14, wherein the reaction is carried out in an inert environment and at -40 ° C to 200 ° C. The process according to any one of claims 1 to 15, wherein the reaction is carried out in the presence of a solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, and combinations thereof. Formula (II)

A compound of
Where
Each 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 fluoro, chloro, bromo, iodo and -OR ³⁰ [R ³⁰ is an inert functional group selected from ethers of hydrocarbyl or substituted hydrocarbyl] , wherein R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated A compound that forms a ring. A process for producing a dehydrogenated silylation product comprising:
(A) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silyl hydride functional group, and (c) a mixture containing a catalyst, optionally in the presence of a solvent. A step of reacting to produce a dehydrogenated silylation product below, wherein the catalyst is of formula (III):

Complex or adduct thereof,
Where
Each 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 fluoro, chloro, bromo, iodo and -OR ³⁰ [R ³⁰ is an inert functional group selected from ethers of hydrocarbyl or substituted hydrocarbyl] , wherein R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated Forming a ring,
L is hydroxyl or an anionic ligand selected from the group consisting of C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl groups, or component (a) [L is Optionally containing at least one heteroatom),
Y is a neutral ligand, and Q is a non-coordinating anion,
process. The complex body further contain the step of removing from the dehydrogenation silylation products, wherein the dehydrogenation silylation product contains a silane or siloxane containing silyl group and an unsaturated group, The process of claim 18. The molar ratio of the unsaturated group in said component (a) to silylhydride functional group in said component (b), 1: 1 less than or where, said to silylhydride functional group in said component (b) 20. Process according to claim 18 or 19 , wherein the molar ratio of unsaturated groups in component (a) is greater than or equal to 1: 1. 21. A process according to any one of claims 18 to 20 , wherein component (a) is a monounsaturated compound. Component (a) is an olefin, cycloalkene, alkyl-capped allyl polyether, vinyl functionalized alkyl-capped allyl or methallyl polyether, alkyl-capped terminally unsaturated amine, alkyne, terminally unsaturated acrylate or methacrylate, unsaturated arylether 21. Any one of claims 18-20 , selected from the group consisting of: vinyl functionalized polymers or oligomers, vinyl functionalized silanes, vinyl functionalized silicones, unsaturated fatty acids, unsaturated esters, and combinations thereof. Process. Q is [B [3,5- (CF ₃ ) ₂ C ₆ H ₃ ] ₄ ] −, B (C ₆ F ₅ ) ₄ ⁻ , Al (OC (CF ₃ ) ₃ ) ₄ −, and CB ₁₁ H ₁₂ —and a combination thereof, wherein Y is selected from the group consisting of dinitrogen (N ₂ ), phosphines, CO, nitrosyl, olefins, amines, ethers and combinations thereof. A process according to any one of claims 18-22 . Y _{is, PH 3, PMe 3, CO} , NO, ethylene, selected from the group consisting of THF and NH _3, The process of claim 23. The component (a) is N, N-dimethylallylamine, allyloxy substituted polyether, propylene, cyclohexene, linear alpha olefin, internal olefin, branched olefin, unsaturated polyolefin, vinyl siloxane of formula (VIII) and combinations thereof Wherein formula (VIII) is selected from the group consisting of:

And
Wherein the alkyl of each ^{R 8} is independently C1 - C18, a substituted alkyl, vinyl, aryl or substituted aryl, of C1 - C18, n is equal to 0 or greater than or 0, according to claim 22 Process. The component (b) is R _a SiH _4-a , (RO) _a SiH _4-a , HSiR _a (OR) _3-a , R ₃ Si (CH ₂ ) _f (SiR ₂ O) _k SiR ₂ H, _{(RO) 3 Si (CH 2} ) f (SiR 2 O) k SiR 2 H, Q u T v T H p D w D H x M H y M z and is selected from the group consisting of,
Wherein, Q is _{SiO 4/2,} T is R'SiO _3/2, ^{T H} is _{HSiO 3/2,} D is R 'is ₂ SiO _2/2, ^{D H} is R' is HSiO _2/2, ^{M H} is' a _{3-g SiO 1/2,} M is R _{'H g} R a ₃ SiO _1/2, each R and R' are the C1~C18 independently Alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R and R ′ optionally contain at least one heteroatom, each of a independently has a value of 1 to 3, f has a value from 1 to 8, k has a value from 1 to 11, g has a value from 1 to 3, p is from 0 to 20, u is from 0 to 20, v is from 0 20, w is 0 to 1000, x is 0 to 1000, y is 0 to 20, and z is 0 26. A process according to any one of claims 18 to 25, wherein the process is such that p + x + y is equal to 1 to 3000, and the valences of all elements in the silyl hydride are satisfied. 27. The process of claim 26 , wherein p, u, v, y, and z are from 0 to 10 and w and x are from 0 to 100, where p + x + y is equal to 1 to 100. 26. A process according to any one of claims 18 to 25 , wherein component (b) has one of the following structures:
R ¹ _a (R ² O) _b SiH (Formula IX)

Where
Each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, R ⁶ is hydrogen, C1-C18 Alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, x and w are independently greater than or equal to 0 (in formula X, x is at least equal to 1), and a and b are from 0 The condition is an integer of 3 and a + b = 3. Catalyst complexes of the formula _{(III) MeB (C 6 F} 5) 3 - or _{[B [3,5- (CF 3)} 2 C 6 H 3] 4] - or tetrakis (perfluoro-aryl) borate salt 29. A process according to any one of claims 18 to 28 . Complex is fixed on a support, the support is selected from carbon, silica, alumina, MgCl _2, zirconia, polyethylene, polypropylene, polystyrene, poly (aminostyrene), sulfonated polystyrene, from dendrimers and a combination thereof 30. A process according to any one of claims 18 to 29 . The catalyst comprises a liquid precursor containing at least one component selected from the group consisting of a catalyst precursor and an activator , a solvent, a silyl hydride, a compound containing at least one unsaturated group, and combinations thereof. Can be produced in situ by contacting in the presence, wherein the catalyst precursor is of the structural formula (IV)

Represented by
Where
Each 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 fluoro, chloro, bromo, iodo and -OR ³⁰ [R ³⁰ is an inert functional group selected from ethers of hydrocarbyl or substituted hydrocarbyl] , wherein R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated Forming a ring structure,
X ^{is, F -, Cl -, Br} -, I -, CF 3 R 40 SO 3 - or ^R 50 COO ^- is selected from the group consisting of ^{wherein, R 40} is an alkylene group covalently or C1~C6 And R ⁵⁰ is a C1-C10 hydrocarbyl group;
And said _{activator, NaHBEt 3, CH 3 Li,} DIBAL-H, a LiHMDS and reducing agent or alkylating agent is selected from the group consisting a combination thereof, in any one of claims 18 to 30 The process described. 32. A process according to any one of claims 18 to 31 wherein the reaction is carried out in an inert environment and at -40 <0> C to 200 <0> C. 33. A process according to any one of claims 18 to 32, wherein the reaction is carried out in the presence of a solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, and combinations thereof. A process for producing a cross-linked material comprising (a) a silylhydride-containing polymer, (b) a monounsaturated olefin or unsaturated polyolefin or mixtures thereof, and (c) a mixture containing a catalyst, optionally in the presence of a solvent. And reacting to produce a cross-linked material, wherein the catalyst is of formula (I):

Complex or adduct thereof,
Where
Each 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 fluoro, chloro, bromo, iodo and -OR ³⁰ [R ³⁰ is an inert functional group selected from ethers of hydrocarbyl or substituted hydrocarbyl] , wherein R ^{1 to} R ⁵ other than hydrogen optionally contain at least one heteroatom;
Each of R ⁶ and R ⁷ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R ⁶ and R ⁷ optionally contain at least one heteroatom And
Optionally, any two adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a substituted or unsubstituted, saturated or unsaturated Forming a ring,
L is hydroxyl or C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, or component (a), wherein L optionally contains at least one heteroatom. process. The process according to claim 34 , wherein the reaction is carried out in an inert environment and at -40C to 200C. 36. The process of claim 34 or 35 , wherein the reaction is carried out in the presence of a solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, and combinations thereof.