Preparative electrochemical oxidation of cyclic peralkylsilanes

Electrochemical oxidation of silacyclopentadienes (siloles)

“…It was claimed that controlled-potential electrolysis in the presence of added water yielded partial and complete reduction of the diene system, although no stable products could be isolated. Following our investigation of electrochemical oxidation of cyclic polysilicon compounds [10][11][12][13][14][15], we reported the first electrochemical example of preparative electrolysis of 1,1-bis(trimethylsilyl)-2,3,4,5-tetraphenyl-1-silacyclopentadiene [16] under various conditions. The present work extends (Scheme 1) the cyclic voltammetric measurements to 11 other 2,3,4,5-tetraphenyl-1-silacyclopentadienes 1 [1,1-dihydro-(I); 1-chloro-1-hydro(II); 1-chloro-1-phenyl-(III); 1,1-dichloro-(IV); 1-chloro-1-methyl-(V); 1-chloro-1-phenyl-(VI); 1-chloro-1-(phenylacetylene)-(VII); 1,1-dimethyl-(VIII); 1-methyl-1-phenyl-(IX); 1,1-bis(trimethylsilyl)-(X); 1,1-bis(trimethylstannyl)-(XI); four bicyclic compounds of 2,2 0 ,3,3 0 ,4,4 0 ,5,5 0 -octaphenyl bisiloles bonded through Si-Si bonds (1,1 0 -dimethyl-(XII); 1,1 0 -diphenyl-(XIII); 1,1 0 -dibenzyl-(XIV) and 1,1 0 -bis(trimethylstannyl)-(XV), and a spiro derivative XVI].…”

General Concepts and Recent Advances in the Electrochemical Transformation of Chloro‐ and Hydrosilanes

“…The Si − F bond formation has not yet been described starting from hydrosilanes but should proceed analogously to the synthesis of the Si−Cl bond. Starting from tetraalkylsilanes, [46] and cyclosilanes, [172] the Si−F bond formation is described via cleavage of the corresponding Si−C or Si−Si bond in the presence of a fluoride ion. This fluoride ion can be provided, for example, as BF 4 − by the supporting electrolyte.…”

Electrochemical oxidation germacyclopentadienes (germoles)

“…To the best of our knowledge, there is only one paper on the electrochemical behavior of hexaphenylgermole [15], showing one irreversible reduction wave with a half-wave potential of 3.2 V vs AgjAgClO 4 (in DME solution containing 0.1 M Bu 4 -NClO 4 ). Following our previous investigation of the 0022 electrochemical oxidation of cyclic peralkylorganosilicon compounds [16][17][18][19][20][21][22] and siloles [23,24], the present study reports on the cyclic voltammetry (CV) and controlled-potential electrolysis (CPE) results of five substituted 2,3,4,5-tetraphenyl-1-germacyclopentadienes (germoles) (Scheme 1).…”