A 14-VE Platinum(0) Phosphabarrelene Complex in the Hydrosilylation of Alkynes

Abstract

A bulky phosphabarrelene ligand is used in the platinum-catalyzed hydrosilylation of alkynes. High regioselectivities were achieved under mild conditions from an in situ formed catalyst at low catalyst loadings. Furthermore, a rare 14-VE PtL2 complex was isolated, which equally proved to be a highly reactive catalyst precursor.

Experimental and Computational Studies of the Ruthenium-Catalyzed Hydrosilylation of Alkynes: Mechanistic Insights into the Regio- and Stereoselective Formation of Vinylsilanes

“…Alkyne hydrosilylation reactions using soluble transition-metal catalysts have been shown to be some of the most effective ways to synthesize vinylsilanes . In industrial settings, platinum catalysts such as H 2 PtCl 6 (Speier’s catalyst) and Pt 2 [((H 2 CCH)Me 2 Si) 2 O] 3 (Karstedt’s catalyst) have been widely used for the hydrosilylation reaction, but neither homogeneous nor heterogeneous Pt catalysts provide general solutions for controlling regio- and stereoselective formation of vinylsilanes. Takeuchi and co-workers first demonstrated the stereoselective formation of vinylsilane products by modulating different phosphine ligands on soluble Rh catalysts and by using solvents with different polarities .…”

Porous Organic Polymer as a Heterogeneous Ligand for Highly Regio- and Stereoselective Nickel-Catalyzed Hydrosilylation of Alkyne

“…At the same time, other isomers arising from alkene isomerization, alkyne oligmerization, and hydrogenation accompany the Si–H addition process. Over the past several decades, a series of precious metals, such as Pt, Rh, Ru, Pd, and Th, have been used almost exclusively as catalysts for selective alkyne hydrosilylation. From an economical viewpoint, the use of nonprecious metal catalysts for hydrosilylation is more desirable and attractive.…”

Transition-Metal-Catalyzed Stereo- and Regioselective Hydrosilylation of Unsymmetrical Alkynes

“…[37][38] The use of monophosphine ligands significantly facilitated the application of Pt catalysts in the hydrosilylation of alkynes, expanding the applicability to both alkynes and hydrosilanes (Table 1, entries 11-14). [39][40][41][42] In addition to Pt catalysts, Rh catalysts were also widely used in the β-E selective hydrosilylation of terminal alkynes ( 48 showed good catalytic activity in the hydrosilylation of terminal alkynes, and high β-E selectivity were obtained with appropriate alkynes and hydrosilanes. Noteworthy, in these reactions, the variation of substrate, alkyne, and even the addition sequence may have a remarkable effect on the selectivity.…”

“…37,38 The use of monophosphine ligands significantly facilitated the application of Pt catalysts in the hydrosilylation of alkynes, expanding the applicability to both alkynes and hydrosilanes (entries 11-14). [39][40][41][42] In addition to Pt catalysts, Rh catalysts were also widely used in the -E-selective hydrosilylation of terminal alkynes (Table 1, filled with light purple). Many classic Rh catalysts, such as Rh halides paired with phosphine ligands (PR 3 ) (entries 15-18) [43][44][45][46][47] and carbonyl Rh compounds (entry 19), 48 showed good catalytic activity in the hydrosilylation of terminal alkynes, and high -E-selectivity were obtained with appropriate alkynes and hydrosilanes.…”