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EP-4077339-B1 - CATALYST PARTICLES AND METHODS FOR DEHYDROGENATIVE SILYLATION

EP4077339B1EP 4077339 B1EP4077339 B1EP 4077339B1EP-4077339-B1

Inventors

  • WITKER, David Lawrence

Dates

Publication Date
20260513
Application Date
20201217

Claims (13)

  1. A method of preparing an organosilicon compound, said method comprising: preparing the Ru(0) complex by combining a triruthenium complex and a ligand precursor compound comprising (i) a phosphorous compound; (ii) an amine compound; or (iii) both (i) and (ii) to give the Ru(0) complex in a carrier fluid heating the mixture at a temperature between 50 and 200 °C, to nucleate the Ru(0) complex and give catalyst particles in the carrier fluid; optionally, isolating the catalyst particles from the carrier fluid; and reacting via dehydrogenative coupling (A) an organohydridochlorosilane compound and (B) an alkene compound in the presence of (C) a catalyst, thereby preparing the organosilicon compound; wherein the catalyst (C) comprises the catalyst particles and wherein the carrier fluid comprises a solvent, an oil, a fluid, or combinations thereof;, and wherein components (A) and (B) are added to the preformed catalyst particles (C).
  2. The method of claim 1, wherein: (i) the Ru(0) complex comprises a triruthenium complex; (ii) the Ru(0) complex comprises a phosphorous ligand; (iii) the Ru(0) complex comprises an amine ligand; or (iv) any combination of (i)-(iii).
  3. The method of claim 2, wherein the Ru(0) complex comprises the phosphorous ligand, and wherein: (i) the phosphorous ligand has the general formula PR" 3 , where each R" is independently of formula -R' or -OR', and each R' is an independently selected from aryl groups, aralkyl groups, or cycloalkyl groups; (ii) the phosphorous ligand comprises a Tolman Electronic Parameter of from 2,060 to 2,090 cm -1 ; (iii) the phosphorous ligand comprises a Tolman Cone Angle of from 115 to 185°; or (iv) any combination of (i)-(iii).
  4. The method of claim 4, wherein: (i) the triruthenium complex is Ru 3 (CO) 12 or a derivative thereof; (ii) the triruthenium complex or derivative thereof and the ligand precursor compound are combined in the presence of the carrier fluid to give the Ru(0) complex in combination with the carrier fluid, thereby preparing the mixture; or (iii) both (i) and (ii).
  5. The method of claim 4, wherein the ligand precursor compound comprises the phosphorous compound, and wherein: (i) the phosphorous compound comprises an organophosphine or organophosphite; (ii) the phosphorous compound is selected from triarylphosphines, tricycloalkylphosphines bis(diarylphosphino)alkanes, bis(dicycloalkylphosphino)alkanes, triarylphosphites, and combinations thereof; or (iii) both (i) and (ii).
  6. The method of any one of claims 1-6, wherein the catalyst particles are free from any support material on which the Ru(0) complex nucleates.
  7. The method of any one of claims 1-7, wherein: (i) the elevated temperature is from 80 to 200 °C; (ii) the mixture is heated at the elevated temperature step-wise to a target temperature; (iii) the mixture is mixed prior to and/or during heating the mixture; (iv) the carrier fluid comprises an aromatic solvent; (v) the method further comprises selectively controlling average particle size of the catalyst particles; or (vi) any combination of (i) to (v).
  8. The method of any one of claims 1-8, wherein the method includes isolating the catalyst particles from the carrier fluid, and wherein isolating the catalyst particles comprises: (I) centrifuging the catalyst particles in the carrier fluid to give a sediment comprising the catalyst particles and supernatant comprising the carrier fluid; (II) separating the sediment from the supernatant, thereby isolating the catalyst particles; and optionally, (III) purifying the catalyst particles isolated in (II) via differential centrifugation by repeating (I) and (II).
  9. The method of any one of claims 1-9, wherein the alkene compound (B) is ethylene, and wherein: (i) the organohydridochlorosilane compound (A) comprises chlorodimethylsilane and the organosilicon compound comprises chlorodimethylvinylsilane; (ii) the organohydridochlorosilane compound (A) comprises dichloromethylsilane and the organosilicon compound comprises dichloromethylvinylsilane; of (iii) both (i) and (ii).
  10. The method of any one of claims 1-10, wherein dehydrogenative coupling of components (A) and (B) is carried out in the presence of (D) an olefin compound different from the alkene compound (B) and having an aliphatic unsaturated group.
  11. The method of any one of claims 1-11, wherein the organosilicon compound is prepared in a reaction product comprising a catalyst residue, and wherein the method further comprises: isolating the catalyst residue from the reaction product; and optionally, using the catalyst residue to catalyze a further dehydrogenative coupling reaction.
  12. The method of any one of claims 1-12, wherein dehydrogenative coupling is carried out: (i) at an elevated temperature greater than 60 °C; (ii) at an elevated pressure from greater than atmospheric pressure to 10 bar; (iii) at a molar ratio of alkene compound (B) to organohydridochlorosilane compound (A) of from 1 to 10 (B):(A); (iv) in the presence of a solvent; or (v) any combination of (i) to (iv).
  13. The method of any one of claims 1-13, having: (i) a conversion of the organohydridochlorosilane compound (A) of at least 95%; (ii) a yield of the organosilicon compound of at least 75%; (iii) a selectivity for dehydrogenative silylation (DHS) versus hydrosilylation (DS) of at least 70:30 (DHS:DS); or (iv) any combination of (i) to (iii).

Description

FIELD OF THE INVENTION The present disclosure relates to methods of preparing catalyst particles for dehydrogenative silylation reactions and methods relating to preparing and using the same for preparing vinylsilanes via dehydrogenative silylation. DESCRIPTION OF THE RELATED ART Hydrosilylation reactions are generally known in the art and involve an addition reaction between silicon-bonded hydrogen and aliphatic unsaturation. Hydrosilylation reactions are utilized in various applications, such as for crosslinking components of curable compositions. Hydrosilylation reactions may also be utilized to prepare individual components or compounds, e.g. components for inclusion in such curable compositions. Typically, hydrosilylation reactions are carried out in the presence of a platinum metal-based catalyst due to its excellent catalytic activity and stability. While platinum metal is generally much more expensive than other metals with lesser catalytic activities, non-platinum catalysts suffer from instability when exposed to ambient conditions. In particular, non-platinum catalysts can be prone to undesirable side reactions with ambient oxygen and water, thereby limiting use and potential end applications thereof. Like hydrosilylation reactions, dehydrogenative silylation reactions are also known in the art and similarly involve a reaction between a silicon-bonded hydrogen and aliphatic unsaturation. However, in dehydrogenative silylation, there is no addition reaction, and instead the aliphatic unsaturation is vinylically bonded to silicon. As such, dehydrogenative silylation reactions may be utilized to prepare unsaturated compounds (e.g. olefin functional compounds) which may further undergo additional functionalization and/or coupling reactions (e.g. via hydrosilylation). Unfortunately, catalysts for dehydrogenative silylation reactions suffer many of the same drawbacks associated with hydrosilylation catalysts, such as sensitivity to oxygen, water, and even light. Moreover, while such drawbacks have been overcome with recent advances in hydrosilylation catalyst, many catalytic systems suitable for hydrosilylation reactions are not practical for use in dehydrogenative silylation reactions. For example, many such catalysts exhibit selectivity favoring the addition reaction, especially for minimally substituted olefins, thus leading to unselective reactions with undesirable product mixtures and low yields. Additionally, many conventional dehydrogenative silylation conditions are not functional group tolerant, and thus are limited in application. BRIEF SUMMARY There is provided a method of preparing catalyst particles (the "preparation method"). The preparation method comprises combining a Ru(0) complex by combining a triruthenium complex and a ligand precursor compound comprising (i) a phosphorous compound; (ii) an amine compound; or (iii) both (i) and (ii) to give the Ru(0) complex in a carrier fluid to form a mixture, and heating the mixture at an elevated temperature between 50 and 200 °C, to nucleate the Ru(0) complex and give the catalyst particles in the carrier fluid. The preparation method optionally comprises isolating the catalyst particles from the carrier fluid. The present disclosure provides a method of preparing an organosilicon compound with the catalyst particles prepared by the above method (the "synthesis method"). The synthesis method comprises reacting via dehydrogenative coupling (A) an organohydridochlorosilane compound and (B) an alkene compound in the presence of (C) a catalyst comprising the catalyst particles, thereby preparing the organosilicon compound; wherein the catalyst (C) comprises the catalyst particles and wherein the carrier fluid comprises a solvent, an oil, a fluid, or combinations thereof; and wherein components (A) and (B) are added to the preformed catalyst particles. Specific embodiments of the invention are set forth in the dependent claims. The following documents may be useful in further understanding the invention. VOGEL W ET AL: "Oxygen and carbon monoxide interaction on novel clusters like ruthenium: a WAXS study", JOURNAL OF CATALYSIS, ACADEMIC PRESS, DULUTH, MN, US, vol. 232, no. 2, 10 June 2005 (2005-06-10), pages 395-401; MAGER NATHALIE ET AL: "Synthesis of water-soluble ruthenium clusters by reaction with PTA (1,3,5-triaza-7-phosphaadamantane)", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 794, 1 October 2015 (2015-10-01), pages 48-58; FONTAL BERNARDO ET AL: "Catalytic studies with ruthenium clusters substituted with diphosphines", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL., vol. 149, no. 1-2, 1 December 1999 (1999-12-01), pages 75-85; OJIMA I ET AL: "The reactions of hydrosilanes with trifluoropropene and pentafluorostyrene catalysed by ruthenium, rhodium and palladium complexes", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 260, no. 3, 17 January 1984 (1984-01-17), pages 335-346; and WO 2019/138194 A1 all disclose catalyst particles and methods of preparing