Catalyst particles and methods for dehydrogenative silylation

Patent metadata

Field	Value
Publication number	US-12371446-B2
Application number	US-202017786571-A
Country	US
Kind code	B2
Filing date	Dec 17, 2020
Priority date	Dec 18, 2019
Publication date	Jul 29, 2025
Grant date	Jul 29, 2025

Abstract

A method of preparing catalyst particles (the “preparation method”) is disclosed. The preparation method comprises combining a Ru(0) complex and a carrier fluid to form a mixture and heating the mixture at an elevated temperature 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. A method of preparing an organosilicon compound via dehydrogenative silylation with the catalyst particles (the “synthesis method”) is also disclosed. The synthesis method comprises reacting (A) an organohydridochlorosilane compound and (B) an alkene compound in the presence of (C) a catalyst, thereby preparing the organosilicon compound. The catalyst (C) of the synthesis method comprises the catalyst particles prepared by the preparation method.

First claim

The invention claimed is:

1. A method of preparing an organosilicon compound, said method comprising:
preparing a Ru (O) complex by combining a triruthenium complex and a ligand precursor compound to give the Ru(0) complex:
heating a mixture of the Ru(0) complex in a carrier fluid at an elevated temperature 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) unsubstituted ethylene in the presence of (C) a catalyst, thereby preparing the organosilicon compound:
wherein the catalyst (C) comprises the catalyst particles;
wherein (i) the triruthenium complex comprises Ru 3 (CO) 12 ;
wherein the ligand precursor compound comprises: (i) a phosphorous compound; (ii) an amine compound; or (iii) both (i) and (i); 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; or (ii) both (i) and (ii).

2. The method of claim 1 , wherein the triruthenium complex 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.

3. The method of claim 1 , 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 substituted or unsubstituted triarylphosphines, tricycloalkylphosphines bis (diary phosphino)alkanes, bis(dicycloalkylphosphino)alkanes, triarylphosphites, and combinations thereof; or (iii) both (i) and (ii).

4. The method of claim 1 , wherein the catalyst particles are free from any support material on which the Ru(0) complex nucleates.

5. The method of claim 1 , 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: (i) 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).

6. The method of claim 1 , comprising 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; and
(II) separating the sediment from the supernatant, thereby isolating the catalyst particles; and
(III) optionally, purifying the catalyst particles isolated in (II) via differential centrifugation by repeating (I) and (II).

7. The method of claim 1 , wherein dehydrogenative coupling of components (A) and (B) is carried out further in the presence of (D) an olefin compound different from the component (B) and having an aliphatic unsaturated group.

8. The method of claim 1 , 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.

9. The method of claim 1 , 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 component (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).

10. The method of claim 1 , 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).

Assignees

• Dow Silicones Corp

Inventors

• Witker David Lawrence

Classifications

• B01J35/23

  in a colloidal state · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J2531/821

  Ruthenium · CPC title

• B01J37/009

  Preparation by separation, e.g. by filtration, decantation, screening · CPC title

• B01J31/2404

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring · CPC title