Nonheme binuclear transition metal complexes with hydrosulfide and polychalcogenides.

The intriguing chemistry of chalcogen (S, Se)-containing ligands and their capability to bridge multiple metal centres have resulted in a plethora of reports on transition metal complexes featuring hydrosulfide (HS) and polychalcogenides (E, E = S, Se). While a large number of such molecules are strictly organometallic complexes, examples of non-organometallic complexes featuring HS and E with N-/O-donor ligands are relatively rare. The general synthetic procedure for the transition metal-hydrosulfido complexes involves the reaction of the corresponding metal salts with HS/HS and this is prone to generate sulfido bridged oligomers in the absence of sterically demanding ligands.

Transition Metal Mediated Hydrolysis of C-S Bonds: An Overview of a New Reaction Strategy.

Desulfurization of organosulfur substrates is highly important due to its relation with the industrial hydrodesulfurization (HDS) process of fossil fuels, which helps to eliminate the sulfur-containing impurities such as thiols, sulfide, thiophenes, etc. from crude oil for the production of easily processed and more cleanly combusted fuel with very low sulfur content. While the HDS process involves a hydrogenolysis reaction under a high pressure of hydrogen gas at high temperature, the hydrolysis of C-S bonds of organosulfur substrates at ambient conditions may very well be considered as a potential alternative for model desulfurization reactions.

Hydrolysis and Transfer Reactivity of the Coordinated Thiolate, Thiocarboxylate, and Selenolate in Binuclear Zinc(II) Complexes.

A new binuclear Zn(II) complex, [Zn(PhBIMP)(DMF)] () (where PhBIMP is the anion of 2,6-bis[bis[(-methyl-4,5-diphenylimidazoylmethyl)amino]methyl]-4-methylphenol), has been shown for the first time to mediate the hydrolytic C-S bond cleavage of a series of aliphatic and aromatic thiolates to yield the corresponding alcohols/phenols along with the formation of a hydrosulfide-bridged complex, [Zn(PhBIMP)(μ-SH)(DMF)] (), which has been thoroughly characterized in comparison with the corresponding chloride complex, [Zn(PhBIMP)(Cl)(DMF)] (), as a control. The binuclear Zn(II)-thiolate complexes [Zn(PhBIMP)(μ-SR)] (R = Ph, ; 3-Br-CH, ) have also been synthesized by avoiding the C-S bond cleavage reaction. Based on the experimental results for the effects of HO and EtN on , , and , the complex [Zn(PhBIMP)(μ-SR)(OH)] has been proposed to be the active intermediate that precedes the C-S bond cleavage of thiolates.

Catalytic Hydrolysis of Thiolates to Alcohols.

A new and efficient catalytic hydrolysis of aliphatic and aromatic thiolates under ambient conditions is presented. Previously, we have demonstrated (Ganguly et al., .