New Vinylgermanium Derivatives of Silsesquioxanes and Their Ruthenium Complexes—Synthesis, Structure, and Reactivity

Abstract

New vinylgermanium cubic derivatives of silsesquioxanes (i.e., monovinylhepta(alkyl, phenyl)-germasilsesqiuoxanes and (dimethylvinylgermoxy)-heptaisobutylsilsesquioxanes) were synthesized and characterized by spectroscopic methods. The first ruthenium− germasilsesquioxyl complexes were also prepared via stoichiometric reaction of RuHCl(CO)(PPh 3 ) 3 with the abovementioned vinylgermanium derivatives of silsesquioxanes, and their structures were determined by spectroscopic and X-ray analyses. The initial ruthenium complex as well as the above-mentioned Ge−Ru complexes were tested as catalysts, in the germylative coupling with olefins, and proved to be active in the case of (dimethylvinyl)-germoxyheptaisobutylsilsesquioxane but showed no activity toward vinylgermasilsesquioxanes. A general mechanism for the germylative coupling of the two vinylgermanium derivatives of silsesquioxanes is presented.

Introduction of Boron Functionalities into Silsesquioxanes: Novel Independent Methodologies

“…The conversion was determined by NMR spectroscopy.T he resultso fN MR analysis( in particular 13 Cs pectra) led to the conclusion that the main product of the mixture was ad i-substituted derivative, whereas the tri-substituted one was obtained only in small amounts. mixture of products was observed.…”

“…The structure of products was determined by NMR spectroscopy.T he spectra 1 H, 13 Ca nd 29 Si NMR were recorded on the Bruker ASCEND 400 (400 MHz) spectrometer using C 6 D 6 as the solvent. POSS compounds were obtained from Hybrid Plastics.…”

“…[1][2][3][4][5][6][7][8] In this connection, they have been extensively investigated, especially in materialc hemistry. [13][14][15][16][17] Traditionally,c onventional methods using halo-compounds are used to modify their structure, [18][19][20][21][22] however catalytic solutionsa re becoming increasingly investigated. [13][14][15][16][17] Traditionally,c onventional methods using halo-compounds are used to modify their structure, [18][19][20][21][22] however catalytic solutionsa re becoming increasingly investigated.…”

Vinyl‐Functionalized Silsesquioxanes and Germasilsesquioxanes

“…The first stage of our study was to develop efficient synthetic methods for the preparation of chlorovinylgermanes, which, in contrast to their silicon analogues, are not commercially available. Chloroarylvinyl‐ and chloroalkylvinylgermanes can be synthesized by the transmetalation of chlorogermanes with organotin reagents in the presence of a radical initiator . These reactions were performed in an inert gas atmosphere (Ar) through vacuum‐ line and standard Schlenk techniques owing to the sensitivity of the reagents.…”

“…Chloroarylvinyl-and chloroalkylvinylgermanes can be synthesized by the transmetalation of chlorogermanes with organotin reagents in the presence of a radical initiator. [19][20][21] These reactions were performed in an inert gas atmosphere (Ar) through vacuum-line and standard Schlenk techniques owing to the sensitivity of the reagents. The next step was the condensation of the POSS silanols and the respective chlorovinyl metalloids.…”