Issue 34, 2018

Heptamolybdate: a highly active sulfide oxygenation catalyst

Abstract

The sulfide oxygenation activities of both heptamolybdate ([Mo7O24]6−, [1]6−) and its peroxo adduct [Mo7O22(O2)2]6− ([2]6−) were examined in this contribution. [Mo7O22(O2)2]6− was prepared in a yield of 65% from (NH4)6[Mo7O24] (1a) upon treatment of 10 equiv. of H2O2 and structurally identified through single crystal X-ray diffraction study. (nBu4N)6[Mo7O22(O2)2] (2b) is an efficient catalyst for the sequential oxygenation of methyl phenyl sulfide (MPS) by H2O2 to the corresponding sulfoxide and subsequently sulfone with a 100% utility of H2O2. Surprisingly, (nBu4N)6[Mo7O24] (1b) is a significantly faster catalyst than 2b for MPS oxygenation under identical conditions. The pseudo-first order kcat constants from initial rate kinetics are 54 M−1 s−1 and 19 M−1 s−1 for 1b and 2b, respectively. Electrospray ionization mass spectrometry (ESI-MS) investigation of 1b under the catalytic reaction conditions revealed that [Mo2O11]2− is likely the main active species in sulfide oxygenation by H2O2.

Graphical abstract: Heptamolybdate: a highly active sulfide oxygenation catalyst

Supplementary files

Article information

Article type
Paper
Submitted
11 fev 2018
Accepted
24 may 2018
First published
24 may 2018

Dalton Trans., 2018,47, 11882-11887

Author version available

Heptamolybdate: a highly active sulfide oxygenation catalyst

A. G. Porter, H. Hu, X. Liu, A. Raghavan, S. Adhikari, D. R. Hall, D. J. Thompson, B. Liu, Y. Xia and T. Ren, Dalton Trans., 2018, 47, 11882 DOI: 10.1039/C8DT00583D

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