Vanadium-substituted polymolybdates and polytungstates were screened as catalysts for the air-based oxidation of thiols under ambient conditions. No noteworthy activity was observed. The same is true for aqueous Cu(II) alone. However, vanadium-substituted polymolybdates (PMo12-nVnO40(3+n)- ) together with micromolar quantities of Cu(II), e.g. Cu(ClO4)2, act synergistically to catalyze the efficient aerobic oxidation of a representative thiol, 2-mercaptoethanol. The catalytic activity increases with the number of vanadium atoms, n, in polymolybdates. PMo6V6O409- together with Cu(II) is the most active co-catalytic system. In acetonitrile, 30 mM 2-mercaptoethanol is completely oxidized under air at room temperature in 3 hours in the presence of 0.5 mM Cu(ClO4)2, and 0.1 mM (TBA)5H4[PMo6V6O40] achieving a TON ≈ 3x102. The reaction stoichiometry, 4 CH2(OH)CH2SH per 1 eq of O2 indicates that the disulfide, (HOCH2CH2S-)2, is the main product, a result confirmed by NMR. The results of extensive kinetic studies, including stopped-flow experiments, and the mechanistic conclusions therefrom, will be discussed.

Synergism of Keggin-type heteropolyanions PMo12-nVnO40(3+n)- and Cu(II) in catalysis of aerobic thiol oxidation

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.