22538-45-0Relevant academic research and scientific papers
DEHYDROGENATIVE SILYLATION, HYDROSILYLATION AND CROSSLINKING USING PYRIDINEDIIMINE COBALT CARBOXYLATE CATALYSTS
-
Page/Page column 58; 59, (2017/02/24)
A process for producing a silylated product comprises reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, to produce a dehydrogenative silylated product, a hydrosilylated product, or a combination of a dehydrogenative silylated product and a hydrosilylated product, wherein the catalyst is chosen from a pyridine diimine cobalt dicarboxylate complex or a cobalt carboxylate compound, and the process is conducted without pre-activating the catalyst via a reducing agent and/or without an initiator or promoter compound. The present catalysts have been found to be active in the presence of the silyl hydride employed in the silylation reaction.
Bench-Stable, Substrate-Activated Cobalt Carboxylate Pre-Catalysts for Alkene Hydrosilylation with Tertiary Silanes
Schuster, Christopher H.,Diao, Tianning,Pappas, Iraklis,Chirik, Paul J.
, p. 2632 - 2636 (2016/04/26)
High-spin pyridine diimine cobalt(II) bis(carboxylate) complexes have been synthesized and exhibit high activity for the hydrosilylation of a range of commercially relevant alkenes and tertiary silanes. Previously observed dehydrogenative silylation is suppressed with the use of sterically unencumbered ligands, affording exclusive hydrosilylation with up to 4000 TON. The cobalt precatalysts were readily prepared and handled on the benchtop and underwent substrate activation, obviating the need for external reductants. The cobalt catalysts are tolerant of epoxide, amino, carbonyl, and alkyl halide functional groups, broadening the scope of alkene hydrosilylation with earth-abundant metal catalysts.
CATALYSIS OF HYDROSILYLATION. VII. CATALYSIS OF HYDROSILYLATION OF C=C BONDS BY RUTHENIUM PHOSPHINE COMPLEXES
Marciniec, Bogdan,Gulinski, Jacek
, p. 349 - 362 (2007/10/02)
A full account of the catalysis of hydrosilylation of the C=C bond in olefins, their derivatives with functional groups as well as in vinyl-trisubstituted silanes by ruthenium(II) and ruthenium(III) phosphine precursors is given.The ruthenium complexes are far more efficient catalysts for the hydrosilylation of 1-alkenes and vinyl-substituted silanes than for the substituted olefins and unsaturated esters.General features characterizing all hydrosilylation reactions catalyzed by the above catalysts are as follows: the reaction proceeds with alkoxy-substituted silanes(also with vinylsilanes) in the absence of solvent, and is enhanced (for RuII and olefins occurs exclusively) in the presence of molecular oxygen.Two general mechanisms are proposed for hydrosilylation of olefins and of vinylsilanes, respectively, which account for most of the experimental observations.
