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

Результат исследования: Научные публикации в периодических изданияхстатьярецензирование

2 Цитирования (Scopus)


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.

Язык оригиналаанглийский
Номер статьи119645
Число страниц8
ЖурналInorganica Chimica Acta
СостояниеОпубликовано - 1 авг 2020


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