Step wise and dissociative mechanisms of the electron transfer in electrochemical reactions involving organosilicon compounds: Molecular-thermodynamic approach1 |
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Authors: | V V Zhuikov |
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Institution: | (1) Kazan State University, ul. Lenina 18, Kazan, 420008 Tatarstan, Russia |
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Abstract: | Electrochemical reduction of organochlorosilanes and oxidation of hexaorganodisilanes may occur via dissociative and stepwise
mechanisms, the choice between which is determined by the balance between fundamental structural parameters of elementoorganic
molecules. The formation of radical anions of silyl-substituted chloromethane in the conditions of an electrochemical experiment
is shown. The formation is due to α-silicon stabilization of the intermediate during the electron transfer. The role of conjugation
and hyperconjugation in the organosilicon compounds’ reactivity is analyzed.
When employing terms “ stepwise ” and “ dissociative ” mechanisms of the electron transfer, we follow tradition introduced
and developed by J.-M. Saveant’s group 1] and recommended by the IUPAC Commission on Electrochemical Nomenclature 2]. The
terms refer to an electrochemically reversible transfer of electron whose kinetics does not limit the process rate as a whole
and to an electrochemically irreversible transfer which involves a bond cleavage in an elementary act of electron transfer.
The term “ activation ” mechanism, which is sometimes applied to electrochemically irreversible processes, is more universal;
however, it is somewhat not unique as compared with the term “ dissociative.” Coupled with “ associative,” the latter may
be used for indicating processes that involve the formation of a bond in an elementary act of electron transfer. |
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