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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. [ABSTRACT FROM AUTHOR]

A new catalytic system, based on an octacarbonyl dicobalt(0) complex and bulky ligand, providing a route to α-vinylgermanes is described. The proposed method can be effectively used for Markovnikov-selective hydrogermylation of a number of terminal and internal alkynes. It has been proved that analogous catalytic systems containing less sterically demanding ligands cannot serve as selective catalysts in this transformation.

The first metal-free protocol for efficient synthesis of unsymmetric bis(thioesters) via functionalization of dithiols with two different α,β-unsaturated aldehydes is presented. The methodology described leads to a novel class of dithiol-based building blocks.

A new cobalt complex bearing a bulky N-heterocyclic carbene (NHC) ligand is described as a pre-catalyst for alkyne hydroboration. The proposed catalytic system, synthesized using easily accessible reagents, allowed obtaining a series of mono- and dialkenylboranes in solvent-free conditions with excellent efficiency and selectivity. The results have been compared to those obtained in the presence of the same cobalt complex containing smaller NHC ligands and those achieved for the catalytic system based on a CoCl 2 - NHC precursor., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Eight rhodium complexes-including four new compounds-with the generic formula [RhCl(cod)(NHC)] (cod is 1,3-cyclooctadiene) differing by the size of their N-heterocyclic carbene (NHC) ligand were prepared, characterized, and found to be catalytically active in the hydrothiolation of terminal alkynes with aliphatic or aromatic thiols. The steric bulk of the carbene was found to markedly influence the reaction rate and selectivity. In particular, superbulky NHCs led to the almost quantitative formation of the sole α-vinyl sulfide products. The experimental conditions were optimized to allow the straightforward synthesis of a broad range of mono- and disubstituted α-adducts starting from terminal alkynes (18 examples) and thiols (5 examples). Altogether, the procedure devised in this study provides an easy access to α-vinyl sulfides with full atom economy and a low catalyst loading.

A new platinum complex bearing bulky N-heterocyclic carbene ligand of the general formula [Pt(IPr*Ph)(dvtms)] (where IPr*Ph = 1,3-bis{2,4,6-tris(diphenylmethyl)phenyl}imidazol-2-ylidene, dvtms = divinyltetramethyldisiloxane) exhibits a high catalytic activity towards E-selective dimerization of ethynyl substituted siloxysilsesquioxanes. This process leads to a novel class of functionalized silsesquioxane derivatives, resembling their dumbbell-shaped silsesquioxane analogues.

Platinum-N-heterocyclic carbene complex with the formula [Pt(IPr* OMe )(dvtms)] (where IPr* OMe = 1,3-bis{2,6-bis(diphenylmethyl)-4-methoxyphenyl}imidazol-2-ylidene, dvtms = divinyltetramethyldisiloxane) exhibits a high catalytic activity towards the β- E -selective hydrosilylation of terminal acetylenes with many secondary silanes (46 examples). Depending on the ratio of the reagent concentrations, the products of mono- or disubstitution are selectively obtained. Moreover, the one-pot sequential hydrosilylation of two different alkynes with secondary silane was also achieved over the same platinum catalyst., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Ruthenium-N-heterocyclic carbene complexes with the generic formula [RuHCl(CO)(NHC)(PCy3)] exhibit a high catalytic activity toward the (E)-selective silylative coupling of divinyl-substituted double-decker silsesquioxanes with two distinctly substituted styrenes. This process leads to a novel class of unsymmetrically functionalized silsesquioxane derivatives.

Amidobenzylidene ruthenium chelates - latent catalysts of olefin metathesis can be easily activated by the addition of Brønsted or Lewis acids. Their activation in the presence of hydrogen chloride involves the formation of catalytically active trans-dichloro carbamatobenzylidene ruthenium chelates.

The first ruthenium-silsesquioxyl complexes have been synthesised and characterized via spectroscopic and X-ray methods. Mechanistic studies were performed and the complexes obtained were proved to be intermediates in the catalytic cycle of silylative coupling of olefins with vinylsilsesquioxane. Moreover, a mechanism for silylative coupling of styrene with vinylsilsesquioxanes was proposed.