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Cryoelectrochemical reduction of a phenyl sulfide in tetrahydrofuran: mediated reduction gives different products compared to direct reduction
Author(s) -
Burasov Alexander V.,
Paddon Christopher A.,
Bhatti Farrah L.,
Donohoe Timothy J.,
Compton Richard G.
Publication year - 2007
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1138
Subject(s) - chemistry , tetrahydrofuran , electrochemistry , cyclic voltammetry , electron transfer , sulfide , naphthalene , electrolysis , one electron reduction , photochemistry , inorganic chemistry , organic chemistry , electrode , electrolyte , solvent
Abstract An electrocatalytic reduction of [(3‐{[trans‐4‐(methoxymethoxy)cyclohexyl]oxy}propyl)thio]benzene (RSPh) in the presence of naphthalene as a mediator is investigated, using steady‐state voltammetry at various sized platinum microelectrodes and at low temperature (201 K) in tetrahydrofuran (THF). This mediated process has been found to involve the transfer of one electron, in contrast to the direct electrochemical reduction which involves two electrons. In addition, the mediated reduction proceeds at a potential, some 500 mV less negative than the direct electrochemical reduction. The evidence for the proposed mechanism has been obtained from theoretical simulations, using DIGISIM which shows satisfactory fitting to experimental results and allowed the determination of the rate constant for the homogeneous step. In contrast to direct reduction of RSPh where only one product, trans ‐1‐ (methoxymethoxy)‐4‐propoxycyclohexane (RH), has been obtained, the isolation of two products, RH and the dimer, diphenyl disulfide, PhSSPh, following mediated preparative electrolysis of RSPh, in presence of naphthalene shows that this one‐electron process may be carried out at the reduction potential of naphthalene at low temperature and has also validated deductions made from voltammetric results. Copyright © 2007 John Wiley & Sons, Ltd.