Selective Oxidation by H5[PV2Mo10O40] in a Highly Acidic Medium

Chandan Kumar Tiwari, Mark Baranov, Alevtina Neyman, Ronny Neumann, Ira A. Weinstock

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

Dissolution of the polyoxometalate (POM) cluster anion H5[PV2Mo10O40] (1; a mixture of positional isomers) in 50% aq H2SO4 dramatically enhances its ability to oxidize methylarenes, while fully retaining the high selectivities typical of this versatile oxidant. To better understand this impressive reactivity, we now provide new information regarding the nature of 1 (115 mM) in 50% (9.4 M) H2SO4. Data from 51V NMR spectroscopy and cyclic voltammetry reveal that as the volume of H2SO4 in water is incrementally increased to 50%, V(V) ions are stoichiometrically released from 1, generating two reactive pervanadyl, VO2+, ions, each with a one-electron reduction potential of ca. 0.95 V (versus Ag/AgCl), compared to 0.46 V for 1 in 1.0 M aq H2SO4. Phosphorus-31 NMR spectra obtained in parallel reveal the presence of PO43-, which at 50% H2SO4 accounts for all the P(V) initially present in 1. Addition of (NH4)2SO4 leads to the formation of crystalline [NH4]6[Mo2O5(SO4)4] (34% yield based on Mo), whose structure (from single-crystal X-ray diffraction) features a corner-shared, permolybdenyl [Mo2O5]2+ core, conceptually derived by acid condensation of two MoO3 moieties. While 1 in 50% aq H2SO4 oxidizes p-xylene to p-methylbenzaldehyde with conversion and selectivity both greater than 90%, reaction with VO2+ alone gives the same high conversion, but at a significantly lower selectivity. Importantly, selectivity is fully restored by adding [NH4]6[Mo2O5(SO4)4], suggesting a central role for Mo(VI) in attenuating the (generally) poor selectivity achievable using VO2+ alone.

Original languageEnglish
Pages (from-to)11945-11952
Number of pages8
JournalInorganic Chemistry
Volume59
Issue number17
DOIs
StatePublished - 8 Sep 2020

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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