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.

Over the years, hydrosilylation of terminal alkenes has emerged as one of the most prominent applications of homogeneous catalysis. While most of the relevant reports concern β-selective hydrosilylation, yielding linear products which are of industrial importance, the opposite selectivity is also gaining increasing interest and sets the scene for the next challenges. Markovnikov hydrosilylation of alkenes, especially in its asymmetric variant, has become the aim of development of new catalytic systems successfully implementing base-metal complexesone of the most prominent trends in contemporary catalysis. In this Perspective, we present the current state of this topic and the way it has been achieved, with special emphasis put on the issues still unresolved and prospective directions of development based on the trends present in the literature, but without unnecessary attention to some details of only historical significance.

Highly porous foams based on graphene oxide functionalized with branched polyethylenimine are generated and used with unprecedented efficiency for adsorbing heavy metal ions.

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.

Symmetrical 1,1-bis(silyl)ethenes have been easily prepared via ruthenium complex-catalyzed silylative coupling cyclization of 1,2-bis(dimethylvinylsiloxy)ethane to give 2,2,4,4-tetramethyl-3-methylene-1,5-dioxa-2,4-disilacycloheptane with excellent selectivity and good yield, followed by its reaction with Grignard reagents. The cyclic product can also be effectively transformed into cyclic carbosiloxane, 2,2,4,4,6,6,8,8-octamethyl-3,7-dimethylene-1,5-dioxa-2,4,6,8-tetrasilacyclooctane.

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The first example of sodium triethylborohydride-catalysed hydrosilylation of alkenes is reported. The hydrosilylation of certain alkenes, in particular styrenes, vinylsilanes and allyl glycidyl ether, with aromatic hydrosilanes proceeded in a highly regioselective manner to give Markovnikov products. It is significant that several protocols use NaHBEt as a reducing agent generating active catalysts in situ of other hydrosilylation reactions. An anionic mechanism of hydrosilylation is proposed.

A new, efficient protocol for the highly stereoselective one-pot synthesis of (E)-beta-aryl vinyl iodides and (E)-beta-aryl vinyl bromides from styrenes based on sequential ruthenium-catalyzed silylative coupling-N-halosuccinimide-mediated halodesilylation reactions is reported.