TY - JOUR

T1 - Trinuclear M3S4 cluster complexes with hemilabile phosphino-thioether ligands

T2 - Some experimental and theoretical aspects

AU - Gushchin, Artem L.

AU - Shmelev, Nikita Y.

AU - Malysheva, Svetlana F.

AU - Artem'ev, Alexander V.

AU - Belogorlova, Nataliya A.

AU - Abramov, Pavel A.

AU - Laricheva, Yuliya A.

AU - Fomenko, Iakov S.

AU - Piryazev, Dmitriy A.

AU - Sheven, Dmitriy G.

AU - Sokolov, Maxim N.

N1 - Publisher Copyright: © 2020 Elsevier B.V. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/8/1

Y1 - 2020/8/1

N2 - 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.

AB - 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.

KW - DFT calculations

KW - Hemilability

KW - Molybdenum

KW - Phosphine-thioethers

KW - Sulphide clusters

KW - Tungsten

KW - X-ray structure

KW - COORDINATION CHEMISTRY

KW - MO3S4 CLUSTER

KW - TRIOSMIUM CLUSTERS

KW - MECHANOCHEMICAL SYNTHESIS

KW - N-HETEROCYCLIC CARBENES

KW - OXALATE COMPLEXES

KW - 3+2 CYCLOADDITION

KW - TRIANGULAR CLUSTER

KW - TETRANUCLEAR MOLYBDENUM

KW - ELECTRONIC-STRUCTURE

UR - http://www.scopus.com/inward/record.url?scp=85082813930&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2020.119645

DO - 10.1016/j.ica.2020.119645

M3 - Article

AN - SCOPUS:85082813930

VL - 508

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

M1 - 119645

ER -