Hemilability of phosphine-thioether ligands coordinated to trinuclear Mo<sub>3</sub>S<sub>4</sub> cluster and its effect on hydrogenation catalysis
作者:Artem L. Gushchin、Nikita Y. Shmelev、Svetlana F. Malysheva、Alexander V. Artem’ev、Nataliya A. Belogorlova、Pavel A. Abramov、Nikolay B. Kompan’kov、Eric Manoury、Rinaldo Poli、Dmitriy G. Sheven、Rosa Llusar、Maxim N. Sokolov
DOI:10.1039/c8nj03720e
日期:——
coordinated to a Mo atom only via the P atom. All compounds were characterized using 1H and 31P1H} NMR spectroscopy, 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 31P1H} NMR spectroscopy. The spectra indicate equilibrium between cationic [Mo3S4Cl3(PSn)3]+ and neutral [Mo3S4Cl4(PSn)2(PSn*)]
[Mo 3 S 4(tu)8(H 2 O)] Cl 4 ·4H 2 O(tu =硫脲)与(PhCH 2 CH 2)2 PCH 2 CH 2 SR配体的配体交换反应(PS1),戊基(PS2)或Pr(PS3)提供新的络合物,分离为[Mo 3 S 4 Cl 3(PS1)3 ] PF 6([ 1 ] PF 6),[Mo 3 S 4 Cl3( PS2) 3 ] PF 6([ 2 ] PF 6)和[Mo 3 S 4 Cl 3( PS3) 3 ] PF 6([ 3 ] PF 6)盐的收率为30-50%。[ 1 ] PF 6和[ 2 ] PF 6的晶体结构通过X射线衍射(XRD)分析确定。三个膦-硫醚配体中的每一个均以双齿螯合方式与Mo 3 S 4的不同钼原子配位三核簇;本文所用的膦基硫醚配体的所有磷原子位于反式到所述封盖硫(μ 3 -S)。在[Mo 3 S 4(tu)8(H 2 O)] Cl 4 ·4H