Multiply bonded germanium species. Recent developments

Interconversions of the silylene-to-silene and germylene-to-germene types: direct spectroscopic studies and calculations

“…Unexpected transformations were discovered in our study 47 of the products of vacuum pyrolysis of precursors of short-lived 1,1 -di methyl-1 -germene (13), namely, l,l-dimethyl-l-germathietane (14) and l,l,3,3-tetramethyl-l-germacyclobutane (15), by pyrolytic mass spectrometry and matrix IR spectroscopy. The formation of germene 13 upon [2+2l-decomposition of 14 and 15 was expected to occur according to the following Schemes14:…”

Reactions of bis[bis(trimethylsilyl)methyl]germylene and the corresponding stannylene with diazidosilanes

“…After remotal of the solvent, colorless crystals of 4 were obtained (Equation 2). Compound 4 is stable in solution in the absence of air.…”

“…In particular, it has been established that silanimines (Si=N) [l], germanimines (Ge=N) [ 2 ] , and stannanimines (Sn=N) [3] are easily accessiDedicated to Prof. Adrian Gibbs Brook on the occasion of his -'To whom correspondence should be addressed. ble by reactions of silylenes (R2Si:), germylenes (R2Ge:), and stannylenes (R,Sn:) with azides (Equation 1).…”

“…In a recent article [4,5], we reported preparation of N-(azidosily1)germanimines by conversion of bis[bis(trimethylsilyl)methyl]germylene (1) [6] with di-tert-butyl-and dimesityldiazidosilane and reactions of 1 with dimethyl-and diphenyldiazidosilane. Herein, we wish to report the synthesis and structural features of the stable N -(azidosily1)stannanimine (5) which was obtained by treatment of the corresponding stannylene (2) with di-tert-butyldiazidosilane (3) and also the corresponding N-(azidosily1)germanimine (4) prepared and studied in an analogous manner. Furthermore, similar reactions of l and 2 with 1,ldiazidosilanes and with methyl substituted 1,2-and 1,3-diazidosilanes were performed.…”

Synthesis and photochemical reactions of 1,2,7‐chalcogenadistannacycloheptanes

“…see the reviews of Raabe and Michl 1 and Barrau et al 2 Such double-bond species are known to be generated transiently by the thermolysis or the photolysis of 1,3,5-trichalcogenane or 1,2,7-chalcogenadimetallacycloheptane derivatives, as confirmed by trapping reactions with various reagents, 3 -8 a useful method for the synthesis of heterocyclic compounds having Group 14 elements. To the best of our knowledge, however, there is no report on the formation of tin-chalcogen double-bond compounds by the thermolysis or the photolysis of tin-containing heterocyclic compounds.…”