TY - JOUR
T1 - Electrochemical oxidation of three- and four-membered cyclic polysilanes
T2 - (Mes2Si)3 and [t-Bu(Me)Si]4
AU - Zhang, Zeng Rong
AU - Becker, James Y.
AU - West, Robert
N1 - Funding Information:
The authors are grateful to the Israel Science Foundation for financial support.
PY - 1997/1/1
Y1 - 1997/1/1
N2 - The electrochemical oxidation of 1,2,3,4-tetra-tert-butyl-1,2,3,4-tetramethylcyclotetrasilane [t-Bu(Me)Si]4 (I) and hexamesitylcyclotrisilane (Mes2Si)3 (II) in CH2Cl2-CH3CN (4:1 v/v) solutions containing a different electrolyte, under air or argon atmospheres, has been studied. The effects of electrolyte, applied potential and electrode material were investigated. The anodic oxidation of I led to oxygen insertion and gave cyclic siloxanes as the major products. Under specific conditions, in the presence of tetraethylammonium perchlorate or tetrabutylammonium hydrogen sulfate, and under argon atmosphere, the sole product obtained was cyclic siloxane [/-Bu(Me)Si]4O in 94% and quantitative yield, respectively. The electrochemical oxidation of II, unlike that of I, involves ring opening followed by Si - Si bond cleavage and a further reaction with the electrolyte to generate (mostly) linear products of type: X-(Mes2Si)n-Y (n = 1, X; Y = mesityl, H, OH or F).
AB - The electrochemical oxidation of 1,2,3,4-tetra-tert-butyl-1,2,3,4-tetramethylcyclotetrasilane [t-Bu(Me)Si]4 (I) and hexamesitylcyclotrisilane (Mes2Si)3 (II) in CH2Cl2-CH3CN (4:1 v/v) solutions containing a different electrolyte, under air or argon atmospheres, has been studied. The effects of electrolyte, applied potential and electrode material were investigated. The anodic oxidation of I led to oxygen insertion and gave cyclic siloxanes as the major products. Under specific conditions, in the presence of tetraethylammonium perchlorate or tetrabutylammonium hydrogen sulfate, and under argon atmosphere, the sole product obtained was cyclic siloxane [/-Bu(Me)Si]4O in 94% and quantitative yield, respectively. The electrochemical oxidation of II, unlike that of I, involves ring opening followed by Si - Si bond cleavage and a further reaction with the electrolyte to generate (mostly) linear products of type: X-(Mes2Si)n-Y (n = 1, X; Y = mesityl, H, OH or F).
KW - Cyclic polysilanes
KW - Cyclic siloxanes
KW - Electrochemical oxidation
UR - http://www.scopus.com/inward/record.url?scp=0030704403&partnerID=8YFLogxK
U2 - 10.1016/S0013-4686(97)85471-0
DO - 10.1016/S0013-4686(97)85471-0
M3 - Article
AN - SCOPUS:0030704403
SN - 0013-4686
VL - 42
SP - 1985
EP - 1992
JO - Electrochimica Acta
JF - Electrochimica Acta
IS - 13-14
ER -