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.
Fort he first time,o lefin cross metathesis has been developed for vinylgermanium compounds. This paper also marks the first case of transition metal-catalyzed functionalization of heterosilsesquioxanes,w hich in our case are cubic vinylgermasilsesquioxanes and newly synthesizedd i(vinylgermyl)substituted double-decker silsesquioxane.T hese processes leadt oaseries of new molecular, unsaturated mono-a nd divinyl-substituted germasilsesquioxanes, which can be potentially applied as precursors for optoelectronics and for the synthesis of new advanced materials.A dditionally,p reliminary tests of metathetic copolymerization of divinylsubstituted double-deckerd igermasilsesquioxanes (DDSQ-2ViGe) with selected diolefins provedt ob ev ery promising and resulted in the synthesis of novels tereoregular trans-germasilsesquioxyl-vinylene-phenylene macromolecular derivatives.A ll newly obtained compounds were isolated andc haracterized by mass and spectroscopic methods.Scheme5.Cross-metathesis of DDSQ-2ViGe with olefins.
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 the fully regio‐ and stereoselective dimerization of terminal acetylenes.
Series of various dienes, diynes and enynes were hydrosilylated in the presence of platinum complex [Pt(IPr*OMe)(dvms)] (I) (where IPr*OMe=1,3‐bis{2,6‐bis(diphenylmethyl)‐4‐methoxyphenyl}imidazol‐2‐ylidene, dvtms = divinyltetramethyldisiloxane) to afford selectively the corresponding mono‐ and bissilylated products in high yields. In each case, the process proceeded fully regioselectively according to the anti‐Markovnikov rule. Hydrosilylation of carbon–carbon triple bonds led to exclusive formation of E‐isomers. For the first time, a one‐pot sequential hydrosilylation of a selected 1,3‐enyne and symmetric α,ω‐diene with two different silanes was also achieved. Moreover, the optimized reaction conditions were adopted for successful hydrosilylation of 1,3‐enynes with secondary silanes to yield stereoregular polyenes containing terminal carbon–carbon double bonds.
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