Hemilability of phosphine-thioether ligands coordinated to trinuclear Mo3S4 cluster and its effect on hydrogenation catalysis
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Other documents of the author: Gushchin, Artem L.; Shmelev, Nikita Y.; Malysheva, Svetlana F.; Artem’ev, Alexander V.; Belogorlova, Nataliya A.; Abramov, Pavel A.; Kompan’kov, Nikolay B.; Manoury, Eric; Poli, Rinaldo; Sheven, Dmitriy G.; Llusar, Rosa; Sokolov, Maxim
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comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
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Title
Hemilability of phosphine-thioether ligands coordinated to trinuclear Mo3S4 cluster and its effect on hydrogenation catalysisAuthor (s)
Date
2018Publisher
Royal Society of ChemistryISSN
1144-0546; 1369-9261Bibliographic citation
GUSHCHIN, Artem L., et al. Hemilability of phosphine-thioether ligands coordinated to trinuclear Mo 3 S 4 cluster and its effect on hydrogenation catalysis. New Journal of Chemistry, 2018, vol. 42, no 21, p. 17708-17717.Type
info:eu-repo/semantics/articleVersion
info:eu-repo/semantics/submittedVersionSubject
Abstract
Ligand-exchange reactions of [Mo3S4(tu)8(H2O)]Cl44H2O (tu = thiourea) with
(PhCH2CH2)2PCH2CH2SR ligands, where R = Ph (PS1), pentyl (PS2) or Pr (PS3) afford new
complexes isolated as [Mo3S4Cl3(PS1)3]PF6 ([1]PF6), ... [+]
Ligand-exchange reactions of [Mo3S4(tu)8(H2O)]Cl44H2O (tu = thiourea) with
(PhCH2CH2)2PCH2CH2SR ligands, where R = Ph (PS1), pentyl (PS2) or Pr (PS3) afford new
complexes isolated as [Mo3S4Cl3(PS1)3]PF6 ([1]PF6), [Mo3S4Cl3(PS2)3]PF6 ([2]PF6) and
[Mo3S4Cl3(PS3)3]PF6 ([3]PF6) salts in 30-50% yields as the major reaction products. The crystal
structures of [1]PF6 and [2]PF6 were determined by X-ray diffraction (XRD) analysis. Each of
the three phosphine-thioether ligands is coordinated in a bidentate chelating mode to a different
molybdenum atom of the Mo3S4 trinuclear cluster, herewith all the phosphorus atoms of the
phosphino-thioether ligand are located trans to the capping sulfur (3-S). A second product that
forms in the reaction of [Mo3S4(tu)8(H2O)]Cl44H2O with PS1 corresponds to the neutral
[Mo3S4Cl4(PS1)2(PS1*)] complex. Its XRD analysis reveals both bidentate (PS1) and
monodentate (PS1*) coordinating modes of the same ligand. In the latter mode the phosphinethioether
is coordinated to a Mo atom only via the P atom. All compounds were characterized by
1H, 31P{1H} NMR, electrospray-ionization (ESI) mass spectrometry and cyclic voltammetry
(CV). Reactions of [1]PF6, [2]PF6 and [3]PF6 with an excess of Bu4NCl in CD2Cl2 were followed
by 31P{1H} NMR. The spectra indicate equilibrium between cationic [Mo3S4Cl3(PSn)3]
+
and
neutral [Mo3S4Cl4(PSn)2(PSn*)] (n = 1, 2) species. The equilibrium constants were determined
as 2.5 ± 0.2103
, 43 ± 2 М
-1
and 30 ± 2 М
-1
(at 25°C) for [1]PF6, [2]PF6 and [3]PF6, indicating
quantitative differences in hemilabile behavior of the phosphino-thioether ligands, depending on
the substituent at sulfur. Clusters [1]PF6, [2]PF6 and [3]PF6 were tested as catalysts in reduction
of nitrobenzene to aniline with Ph2SiH2 under mild conditions. Significant differencies in the
catalytic activity were observed, which can be attributed to different hemilabile behavior of the
PS1 and PS2/PS3 ligands. [-]
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