Platinum(0) complexes bearing bulky N-heterocyclic carbene ligands, catalyse selective hydrosilylation of terminal olefins as well and internal acetylenes.

Abstract A series of functionalized dialkenylsilsesquioxanes were obtained by efficient and highly stereoselective silylative coupling cross‐metathesis divinylsubstituted double‐decker silsesquioxanes ( DDSQ‐2SiVi ) with substituted styrenes other olefins. Both reactions proceed stereoselectively lead to nearly quantitative formation E isomers. The optimized reaction conditions for styrene adopted successful polycondensation 1,4‐divinylbenzene yielding stereoregular cooligomer containing...

The hydrosilylation of alkynes is one the most attractive and, at same time, challenging catalytic transformations, usually demanding use noble transition metals. We describe a system, based on cobalt(0) complex and bulky N-heterocyclic carbene (NHC) ligands, permitting highly effective broad scope silanes. application NHC ligands allowed decrease in amount cobalt necessary for an reaction run to 2.5 mol% provided excellent selectivity towards α-vinylsilanes. developed method tolerates...

Abstract Monovinylheptaisobutylsilsesquioxane undergoes efficient cross‐metathesis and silylative coupling with styrenes. Allyl derivatives were successfully tested in the presence of first generation Grubbs’ catalyst, while heteroatom‐substituted vinyl (vinyl ethers, 9‐vinylcarbazole) efficiently undergo catalysed by ruthenium hydride complexes. Both reactions proceed highly stereoselectively lead to nearly quantitative formation E isomers. Only when ethers are used does reaction a mixture...

A synthesis of a new macromolecular class vinylene-arylene copolymers with double-decker silsesquioxane in the main chain is presented. Two transition-metal-catalyzed processes, which silylative-coupling copolycondensation (SCC) and ADMET copolymerization divinyl-substituted silsesquioxanes (DDSQ-2SiVi) selected diolefins, are reported to be highly efficient tools for formation stereoregular containing DDSQ-silylene-vinylene-arylene units. The copolymeric products studied terms their...

Synthesis and characterization of new, molecular macromolecular <bold>DDSQ</bold>-based compounds functionalized by substituted styrenes distyrylarenes (also with heteroatoms) in a stereoselective manner is presented.

Abstract New platinum(0) complexes of the general formula [(NHC)Pt(dvtms)] (dvtms=1,3‐divinyltetramethyldisiloxane) containing bulky N‐heterocyclic carbene (NHC) ligands were prepared, characterized, and found to be catalytically active in fully regio‐ stereoselective dimerization terminal acetylenes.

Abstract We present an efficient methodology for the synthesis of tetrafunctionalized double‐decker silsesquioxanes via hydrosilylation reaction. An investigation catalytic system, olefin structure, chemical and steric surrounding Si−H moiety in respective reagent was carried out on progress, selectivity rate process. Two alternative synthetic pathways obtaining a variety functionalized with high yields based Pt catalysts were developed. These parallel routes concern reverse −CH=CH 2...

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 number terminal internal alkynes. It has been proved that analogous systems containing less sterically demanding ligands cannot serve as selective catalysts in this transformation.

Abstract For the first time, olefin cross metathesis has been developed for vinylgermanium compounds. This paper also marks case of transition metal‐catalyzed functionalization heterosilsesquioxanes, which in our are cubic vinylgermasilsesquioxanes and newly synthesized di(vinylgermyl)substituted double‐decker silsesquioxane. These processes lead to a series new molecular, unsaturated mono‐ divinyl‐substituted germasilsesquioxanes, can be potentially applied as precursors optoelectronics...

New vinylgermanium cubic derivatives of silsesquioxanes (i.e., monovinylhepta(alkyl, phenyl)germasilsesqiuoxanes and (dimethylvinylgermoxy)heptaisobutylsilsesquioxanes) were synthesized characterized by spectroscopic methods. The first ruthenium–germasilsesquioxyl complexes also prepared via stoichiometric reaction RuHCl(CO)(PPh3)3 with the above-mentioned silsesquioxanes, their structures determined X-ray analyses. initial ruthenium complex as well Ge–Ru tested catalysts, in germylative...

For the first time, synthesis of thioesters starting from enals and thiols has been performed in presence a bulky N-heterocyclic carbene (NHC) as catalyst.

The [RuHCl(CO)(SIDip)(PCy₃)] complex efficiently catalyzes the (<italic>E</italic>)-selective silylative coupling of divinyl-substituted double-decker silsesquioxanes with two distinctly substituted styrenes.

The [Pt(IPr*^Ph)(dvtms)] complex efficiently catalyzes the <italic>E</italic>-selective dimerization of ethynylsiloxysilsesquioxanes leading to a novel class silsesquioxane derivatives, resembling their dumbbell-shaped analogues.

The regioselectivity of metathesis reactions trisubstituted vinylsilanes H2C═CHSiR3 (SiR3 = SiCl3, SiCl2Me, SiClMe2, SiMe3, Si(OEt)3) with the second-generation ruthenium alkylidene complex has been studied theoretically, by density functional theory (DFT), and experimentally. DFT results indicate that cycloreversion is rate-determining step formation a thermodynamically stable methylidene PhCH═CHSiR3 generally preferred. However, process can be also governed relative stabilities...

Eight rhodium complexes-including four new compounds-with the generic formula [RhCl(cod)(NHC)] (cod is 1,3-cyclooctadiene) differing by size of their N-heterocyclic carbene (NHC) ligand were prepared, characterized, and found to be catalytically active in hydrothiolation terminal alkynes with aliphatic or aromatic thiols. The steric bulk was markedly influence reaction rate selectivity. In particular, superbulky NHCs led almost quantitative formation sole α-vinyl sulfide products....

Pd-based Suzuki–Miyaura coupling reaction leading to a new type of mono- and disubstituted EDOTs is presented. These materials were used synthesize EDOT–SQ systems, which examined for their electrochemical electrochromic properties.

For the first time, ball milling has been employed in solvent-free synthesis of sulfur-functionalized materials from thiols and α,β-unsaturated ketones esters, using potassium carbonate as a transition metal-free catalyst. This environmentally friendly protocol makes use easily accessible reagents to prepare thirty β-sulfenylated carbonyl compounds with yields exceeding 91 % under ambient air conditions. Additionally, this innovative synthetic strategy enables modification chalcones,...

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

Series of various dienes, diynes and enynes were hydrosilylated in the presence platinum complex [Pt(IPr* OMe )(dvms)] ( I ) (where IPr* =1,3‐bis{2,6‐bis(diphenylmethyl)‐4‐methoxyphenyl}imidazol‐2‐ylidene, dvtms = divinyltetramethyldisiloxane) to afford selectively corresponding mono‐ bissilylated products high yields. In each case, process proceeded fully regioselectively according anti‐Markovnikov rule. Hydrosilylation carbon–carbon triple bonds led exclusive formation E ‐isomers. For...

Herein, a facile and efficient synthetic route to unique hybrid materials containing polysiloxanes mono(alkyl)silsesquioxanes as their pendant modifiers (T8@PS) was demonstrated. The idea of this work apply the hydrosilylation reaction tool for selective attachment mono(alkenyl)substituted silsesquioxanes (differing in alkenyl chain length, from -vinyl -dec-9-enyl types inert groups iBu, Ph at inorganic core) onto two various amount Si-H units. protocol, determined confirmed by FT-IR situ...

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 β-E-selective hydrosilylation of terminal acetylenes many secondary silanes (46 examples). Depending on ratio reagent concentrations, products mono- or disubstitution are selectively obtained. Moreover, one-pot sequential two different alkynes silane was...