TY - JOUR
T1 - Novel oxidation processes for the methyltin compounds (CH3)4Sn, (CH3)3SnCl, (CH3)2SnCl2 and CH3SnCl3 at mercury electrodes in dichloromethane
AU - Bond, A. M.
AU - McLachlan, N. M.
PY - 1987/7/24
Y1 - 1987/7/24
N2 - Polarographic and controlled potential electrolysis experiments to define newly observed oxidation processes on mercury electrodes have been conducted on the series of methyltin compounds, (CH3)(4-tnSnCln(n=0-3), in dichloromethane. The processes are associated with oxidation of the mercury electrode and chemical reactions such as methyl and chloride exchange. For (CH3)4Sn the process is chemically irreversible and corresponds to the overall equation, 2(CH3)4Sn+2Hg→(CH3)6 Sn2+2CH3Hg++2e- on the time scale of controlled potential electrolysis experiments. In contrast, alkyltin chloride compounds provide chemically reversible responses at short, voltammetric time scales. These oxidation processes can be described by the stepwise equations (1a) or (1b) or the overall equation (2): {A figure is presented} where n=1-3. On the longer time scale controlled potential electrolysis experiments, inorganic Sn(II) and methylmercuric chloride are identified as products. Unidentified mercury-tin compounds are also believed to be present after controlled potential electrolysis experiments. The stability of the [(CH3)(4-n)Cl(n-1)Sn-Hg=SnCl(n-1) (CH3)(4-n)]2+ complex is markedly lowered as the number of methyl groups present is decreased.
AB - Polarographic and controlled potential electrolysis experiments to define newly observed oxidation processes on mercury electrodes have been conducted on the series of methyltin compounds, (CH3)(4-tnSnCln(n=0-3), in dichloromethane. The processes are associated with oxidation of the mercury electrode and chemical reactions such as methyl and chloride exchange. For (CH3)4Sn the process is chemically irreversible and corresponds to the overall equation, 2(CH3)4Sn+2Hg→(CH3)6 Sn2+2CH3Hg++2e- on the time scale of controlled potential electrolysis experiments. In contrast, alkyltin chloride compounds provide chemically reversible responses at short, voltammetric time scales. These oxidation processes can be described by the stepwise equations (1a) or (1b) or the overall equation (2): {A figure is presented} where n=1-3. On the longer time scale controlled potential electrolysis experiments, inorganic Sn(II) and methylmercuric chloride are identified as products. Unidentified mercury-tin compounds are also believed to be present after controlled potential electrolysis experiments. The stability of the [(CH3)(4-n)Cl(n-1)Sn-Hg=SnCl(n-1) (CH3)(4-n)]2+ complex is markedly lowered as the number of methyl groups present is decreased.
UR - http://www.scopus.com/inward/record.url?scp=50849149886&partnerID=8YFLogxK
U2 - 10.1016/0022-0728(87)80063-3
DO - 10.1016/0022-0728(87)80063-3
M3 - Article
AN - SCOPUS:50849149886
VL - 227
SP - 29
EP - 40
JO - Journal of Electroanalytical Chemistry
JF - Journal of Electroanalytical Chemistry
SN - 1572-6657
IS - 1-2
ER -