Hemilability of phosphine-thioether ligands coordinated to trinuclear Mo₃S₄ cluster and its effect on hydrogenation catalysis

Abstract

Phosphine-thioether ligands were coordinated to the Mo3S4 cluster to afford [Mo3S4Cl3(PS)3]+ complexes. Their catalytic activity in nitrobenzene reduction reflects the different hemilabile behaviours of PS1, PS2 and PS3.

Hemilability and structural considerations in complexes of platinum(II) comprising bis(diphenylphosphanyl)methane monoxide, monosulfide, and monoselenide

“…There are relatively few examples of hemilabile P~S complexes; however, hemilabile phosphine-thioether ligands have been used as hydrogenation catalysts (Gushchin et al, 2018). Although there are reviews on the subject of hemilability (Bader & Lindner, 1991;Braunstein & Naud, 2001;Kwong & Chan, 2008), there is relatively little information on the kinetics of hemilabile systems or the relative ease of dissociation of one donor of a hemilabile ligand in a given system.…”

Slow Inversion of Coordinated Thioether Groups in SNS‐Type Ruthenium Pincer Complexes

“…In chelating ligands thioethers have raised increasing attention as stabilizing σdonating groups for thiophilic transition metals in lower oxidation states [2][3][4] and as hemilabile groups in metal catalysts. [5,6] In particular the utilization of thioether groups in pincer-type ligands led to active catalysts [7] utilized for the hydrogenation of carbonyl compounds or dehydrogenation of alcohols, [8][9][10][11][12][13][14][15][16][17] ester metathesis, [8] alkane transferhydrogenation, [18] cross coupling, [19] cycloaddition [20] and ethylene oligomerization reactions [21][22][23] in recent years.…”