Hydrosilylation and Related Reactions of Silicon Compounds

Highly Diastereo- and Regioselective Transition Metal-Catalyzed Additions of Metal Hydrides and Bimetallic Species to Cyclopropenes: Easy Access to Multisubstituted Cyclopropanes

“…Initially, we tested the hydrosilylaton of disubstituted cyclopropene 1a in the presence of various transition metal catalysts. Our experiments indicated that the employment of nickel, rhodium, and iridium complexes, known to catalyze the addition of H−Si species to unsaturated carbon−carbon bonds, , did not result in the hydrosilylation of cyclopropenes. However, it was found that the hydrosilylation of 1a in the presence of [(π-allyl)PdCl] 2 and a bulky electron-rich TDMPP ligand with trichlorosilane 6a proceeded very selectively from the less hindered face.…”

“…Hydrosilylation of Cyclopropenes. Next, we aimed at expanding this methodology to another as yet unknown hydrometalation reaction on cyclopropenes: hydrosilylation toward cyclopropylsilanes. While cyclopropylsilanes share some reactivity with cyclopropylstannanes, , they also undergo a number of transformations characteristic of organosilanes, including Tamao−Flemming oxidation 28 and the Peterson olefination reaction, which makes them very attractive synthons in their own right.…”

Catalytic activation of remote alkenes through silyl-rhodium(iii) complexes

“…Alkylsilanes are important academic and industrial feedstocks because they are valuable precursors for silicon-based polymers, lubricants and water-repellent coatings, among others. [1][2][3] Focusing on linear alkylsilanes, their common synthesis is through the hydrosilylation of terminal alkenes using platinum catalysts, such as Speier's 4,5 and Karstedt's catalysts. 6 During the last few decades, the hydrosilylation of carboncarbon multiple bonds catalyzed by first-row transition metal compounds has been extensively studied.…”

Enone as a Process Aid for the Highly Efficient Synthesis of Karstedt’s Catalyst: Probing the Mechanism of Dissolution of Platinum(II) Chloride

“…Hydrosilylation reactions between silicon–hydrogen and unsaturated carbon–carbon bonds are widely used in the silicone industry for the preparation of silane monomers and siloxane intermediates and for the cross-linking (curing) of silicone polymers. − While a plethora of catalysts have been developed over the years to promote hydrosilylation reactions, homogeneous platinum-based catalysts such as Speier’s catalyst and Karstedt’s catalyst are still the workhorse reagents for industrial hydrosilylation processes and are often used as the benchmark for evaluations of other hydrosilylation catalysts. − These catalysts are air- and moisture-stable, highly active, and often effective and efficient at just parts per million loading. , …”

“…Formation Enthalpies of Molecular PtCl 2 Complexes (Monomeric and Dimeric Complexes) from PtCl 2 Lattice aΔH formation = E PtCld 2•X − E X − (1/6)E PtCld 2(s)(7) …”