Trinuclear M3S4 cluster complexes with hemilabile phosphino-thioether ligands: Some experimental and theoretical aspects

Artem L. Gushchin, Nikita Y. Shmelev, Svetlana F. Malysheva, Alexander V. Artem'ev, Nataliya A. Belogorlova, Pavel A. Abramov, Yuliya A. Laricheva, Iakov S. Fomenko, Dmitriy A. Piryazev, Dmitriy G. Sheven, Maxim N. Sokolov

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2 Citations (Scopus)

Abstract

Reactions of [W3S4(tu)8(H2O)]Cl4⋅2H2O (tu = thiourea) with (PhCH2CH2)2PCH2CH2SR (R = Ph (PS1) or n-pentyl (PS2), followed by chromatography on silica gel with a solution of KPF6 in acetone as eluent, result in [W3S4Cl3(PS1)3]PF6 ([1]PF6) and [W3S4Cl3(PS2)3]PF6 ([2]PF6) in moderate yields. Crystal structures of [1]PF6 and [2]PF6 were determined by X-ray single crystal analysis. All three phosphine-thioether molecules are bidentately coordinated to tungsten atoms in such a way that the phosphorus atoms are in the trans position to the capping µ3-S atom. The compounds were characterized by 1H, 31P{1H} NMR, and UV–vis spectroscopies and electrospray-ionization mass spectrometry. Unlike similar molybdenum complexes, interaction of [1]PF6 or [2]PF6 with Bu4NCl does not lead to the formation of neutral complexes [W3S4Cl4(PS)2(PS*)] with the monodentate coordination of one of the PS ligands. This indicates weaker hemilabile properties of phosphino-thioether ligands in the tungsten complexes. Consequently, both [1]PF6 and [2]PF6 exhibit significantly lower catalytic activity than the molybdenum analogues in the benchmark reaction of nitrobenzene reduction into aniline with Ph2SiH2. The DFT calculations were performed to determine the relative stability of possible isomers with the chelate, bridging and monodentate manner of coordination of the PS ligands to {M3S4} (M = Mo, W) clusters, taking (CH3)2PCH2CH2SCH3 as a model.

Original languageEnglish
Article number119645
Number of pages8
JournalInorganica Chimica Acta
Volume508
DOIs
Publication statusPublished - 1 Aug 2020

Keywords

  • DFT calculations
  • Hemilability
  • Molybdenum
  • Phosphine-thioethers
  • Sulphide clusters
  • Tungsten
  • X-ray structure
  • COORDINATION CHEMISTRY
  • MO3S4 CLUSTER
  • TRIOSMIUM CLUSTERS
  • MECHANOCHEMICAL SYNTHESIS
  • N-HETEROCYCLIC CARBENES
  • OXALATE COMPLEXES
  • 3+2 CYCLOADDITION
  • TRIANGULAR CLUSTER
  • TETRANUCLEAR MOLYBDENUM
  • ELECTRONIC-STRUCTURE

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