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 ⴱⵕⴰ 2018
Accepted
24 ⵎⴰⵢ 2018
First published
24 ⵎⴰⵢ 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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements