The article provides a comprehensive account of the research on synthetic and catalytic aspects of hydrosilylation. Reactions proceeding in the presence of nucleophilic‐electrophilic catalysts, metals and immobilized metals as well as radical initiators are described. However, particular attention is paid to processes catalysed by transition metal complexes. For these catalytic systems, mechanistic pathways and development of efficient and selective catalytic systems are more comprehensively discussed. Possible applications of hydrosilylation of multiple carbon‐carbon and carbon‐heteroatom bonds in organic and asymmetric synthesis are presented. The article summarizes applications of the hydrosilylation processes in polymer and material chemistry including their contribution in polysiloxane curing, synthesis of new hybrid materials, dendrimers and functionalized molecular and macromolecular organosilicon derivatives.

The cross-metathesis of styrene with various vinylsilanes, H 2 CdC(H)SiR 3 , catalyzed by [Cl 2 (PCy 3 ) 2 RudCHPh] (1) to give (E)-silylstyrene, (E)-Ph(H)CdC(H)SiR 3 , and ethylene is reported. The reaction proceeds even at room temperature and is highly selective. Very high conversions are observed when R ) OEt, OSiMe 3 (g95%, 6 h, 2 mol % of 1). The conversion significantly decreases with increasing substitution of Me for OR′. The metathesis is reversible. Therefore, removal of ethylene is critical for achieving high conversions. From the study of stoichiometric reactions of 1 with vinylsilanes it follows that in the series SiR 3 ) Si(OEt) 3 , SiMe(OEt) 2 , SiMe 2 OEt, SiMe 3 and SiR 3 ) Si(OSiMe 3 ) 3 , SiMe(OSiMe 3 ) 2 , SiMe 2 -(OSiMe 3 ), SiMe 3 the conversion rate increases, but simultaneously the selectivity of the metathesis decreases. The decreasing selectivity readily accounts for the decreasing efficiency in the catalytic metathesis. The product distribution of reactions of styrene-d 8 with H 2 Cd C(H)SiR 3 (R ) OEt, OSiMe 3 ) in the presence of 1 provides evidence for a metallacarbene mechanism involving [Ru]dCHPh and [Ru]dCH 2 species.

A series of neutral ruthenium(II) carbonyl, carbene, vinylidene, and allenylidene complexes [Ru(bdmpza)(Cl)(L)(PPh3)] (L = C(OR‘)R, CCHR, CCCR2, CO) containing the bis(3,5-dimethylpyrazol-1-yl)acetato (bdmpza) ligand, an N,N,O heteroscorpionate ligand, have been prepared. Treatment of [Ru(bdmpza)(Cl)(PPh3)2] (1a) with a variety of alkynes HC⋮CR (R = Ph, Tol, Pr, Bu) afforded the vinylidene complexes [Ru(bdmpza)(Cl)(CCHR)(PPh3)] (2a−d). The carbonyl complex [Ru(bdmpza)(Cl)(CO)(PPh3)] (3) is formed via oxidative or acid-induced degradation pathways from the vinylidene complexes. Reaction of 1a with the hydroxy-functionalized alkynes HC⋮C(CH2) n OH (n = 2, 3) yielded the cyclic Fischer type carbene complexes (4a) and (4b). The ruthenium(II) allenylidene complexes [Ru(bdmpza)(Cl)(CC CR2)(PPh3)] (5a, R = Ph; 5b, R = Tol) were prepared by the reaction of 1a with propargyl alcohols HC⋮CC(R)2OH via the vinylidene intermediates [Ru(bdmpza)(Cl)(CCHCR2OH)(PPh3)]. X-ray crystal structures of one structural isomer of the vinylidene complex [Ru(bdmpza)(Cl)(CCHTol)(PPh3)] (2b), the carbonyl complex [Ru(bdmpza)(Cl)(CO)(PPh3)] (3), the carbene complex (4b - I), and two structural isomers of [Ru(bdmpza)(Cl)(CCCPh2)(PPh3)] (5a - I and 5a-II) are reported.

Selenium NMR has become a standard tool for scaling the p-accepting character of carbenes. Herein, we highlight that non-classical hydrogen bonding (NCHB), likely resulting from hyperconjugation, can play a significant role in the carbene-selenium 77 Se NMR chemical shift, thus triggering a non-linear behavior of the Se-Scale.

The coupling reaction of styrene with vinylsilanes catalyzed by ruthenium complexes was investigated. RuHCl(CO)(PPh3)3 (I) and RuCl(SiR3)(CO)(PPh3)2 (where R3 = Me3 (II), Me2Ph (III), (EtO)3 (IV)) were found to be efficient and selective catalysts for the formation of E-1-phenyl-2-silylethene and evolution of ethene. Stoichiometric reactions of styrene with the Ru−Si bonds of II−IV in argon and silylstyrene with the Ru−H bond in air (I*) as well as a MS study of the product of the deuterated styrene with vinylsilanes are convincing evidence for the mechanism of the process involving the migratory insertion of styrene into the Ru−Si bond (and vinylsilane into Ru−H bond) followed by β-H (and β-Si) elimination to give phenylsilylethene (and ethene). Kinetic tests (TOF) indicate a prior dissociation of the PPh3 molecule (or by its oxygenation) from I to yield pentacoordinated RuHCl(CO)(PPh3)2 which is almost as active as II.

Vinylsubstituted boronates i.e. vinyldioxaborolane and vinyldioxaborinane react regioselectively with olefins in the presence of RuHCl(CO)(PCy3)2 with the formation of functionalized vinylboron derivatives. The reaction opens a new catalytic route for preparation of organoboranes.

Platinum complexes bearing bulky N-heterocyclic carbene (NHC) ligands, i.e., [Pt(IPr*)(dvtms)] (where, IPr* = 1,3-bis{2,6-bis(diphenylmethyl)-4-methylphenyl}imidazol-2-ylidene) and [Pt(IPr*OMe)(dvtms)] (where, IPr*OMe = 1,3-bis{2,6-bis(diphenylmethyl)-4-methoxyphenyl}imidazol-2-ylidene, dvtms = divinyltetramethyldisiloxane) catalyse nearly quantitatively and highly or completely the selective hydrosilylation of terminal olefins as well as terminal or internal acetylenes.

While the formation and breaking of transition metal (TM)–carbon bonds plays a pivotal role in the catalysis of organic compounds, the reactivity of inorganometallic species, that is, those involving the transition metal (TM)–metalloid (E) bond, is of key importance in most conversions of metalloid derivatives catalyzed by TM complexes. This Review presents the background of inorganometallic catalysis and its development over the last 15 years. The results of mechanistic studies presented in the Review are related to the occurrence of TM–E and TM–H compounds as reactive intermediates in the catalytic transformations of selected metalloids (E = B, Si, Ge, Sn, As, Sb, or Te). The Review illustrates the significance of inorganometallics in catalysis of the following processes: addition of metalloid–hydrogen and metalloid–metalloid bonds to unsaturated compounds; activation and functionalization of C–H bonds and C–X bonds with hydrometalloids and bismetalloids; activation and functionalization of C–H bonds with vinylmetalloids, metalloid halides, and sulfonates; and dehydrocoupling of hydrometalloids. This first Review on inorganometallic catalysis sums up the developments in the catalytic methods for the synthesis of organometalloid compounds and their applications in advanced organic synthesis as a part of tandem reactions.