Electrochemical oxidation of cyclic polysilanes under ‘oxygen-free’ and ‘water-free’ conditions

• Published in: Journal of electroanalytical chemistry (Lausanne, Switzerland) Vol. 455; no. 1; pp. 197 - 204
• Main Authors: Zhang, Zeng-Rong, Becker, James Y, West, Robert
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 15.09.1998; Elsevier Science
• Subjects: Chemistry; Cyclic polysilanes; Cyclic siloxanes; Electrochemical oxidation; Electrochemistry; Exact sciences and technology; General and physical chemistry; Kinetics and mechanism of reactions; Cyclic siloxanes; Cyclic polysilanes; Electrochemical oxidation; Silicon heterocycle; Organic silane; Polysilane; Transition metal; Experimental study; Oligomer; Electrodes; Organic solvent; Inorganic heterocycle; Anhydrous medium; Platinum; Acetonitrile; Reaction mechanism; Dichloromethane; Oxidation; Electrochemical reaction
• ISSN: 1572-6657; 1873-2569
• DOI: 10.1016/S0022-0728(98)00209-5

The electrochemical behavior of seven substituted cyclic polysilanes, namely hexamesitylcyclotrisilane (Mes 2Si) 3 (I), 1,2,3,4-tetra- tert-butyltetramethyl-cyclotetrasilane [ t-Bu(Me)Si] 4 (II) (mixture of isomers), decapropylcyclopentasilane (Pr 2Si) 5 ( III) , dodecamethylcyclohexasilane (Me 2Si) 6 ( IV), tetradecaethylcycloheptasilane (Et 2Si) 7 ( V), hexadecamethylcyclooctasilane (Me 2Si) 8 ( VI) and octadecamethylcyclononasilane (Me 2Si) 9 ( VII), have been studied by cyclic voltammetry and preparative electrolysis in ‘oxygen-free’ and ‘water-free’ solutions of CH 2Cl 2+CH 3CN+CF 3COOH (4:1:1) containing sodium trifluoroacetate as the supporting electrolyte. The products are cyclic compounds with one or two oxygen atoms as well as silicon atoms in the rings. The effects of ring size and nature of substituent on the oxidation peak potentials and reactivity of starting materials, and on the selectivity of the outcoming products, are discussed.