A new and efficient catalytic hydrolysis of aliphatic and aromatic thiolates under ambient conditions is presented. Previously, we have demonstrated (Ganguly et al., Inorg. Chem. 2018, 57, 11306–11309) the Co­(II) mediated stoichiometric hydrolysis of thiols to produce alcohols/phenols along with a binuclear dicobalt­(II)-hydrosulfide complex, [Co2(PhBIMP)­(μ2-SH)­(DMF)]2+ (1) (PhBIMP is the anion of 2,6 bis­[(bis­((N-1-methyl-4,5- diphenylimidazoylmethyl) amino)­methyl]- 4-methylphenol). In the present work, we have shown that the product of the stoichiometric reaction, 1, may act as an efficient catalyst for the catalytic hydrolysis of a broad range of aliphatic and aromatic thiolates in DMF at room temperature to produce alcohols/phenols. Complex 1 takes up a thiolate (RS–) and a water molecule to generate an active intermediate complex, [Co2(PhBIMP)­(μ2-SH)­(RS)­(H2O)]1+ (2), which, in turn, releases the alcohol/phenol (ROH), hydrosulfide (HS–), and regenerates 1.

A new binuclear Zn­(II) complex, [Zn2(PhBIMP)­(DMF)2]3+ (1) (where PhBIMP1 is the anion of 2,6-bis­[bis­[(N-1-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, [Zn2(PhBIMP)­(μ-SH)­(DMF)]2+ (2), which has been thoroughly characterized in comparison with the corresponding chloride complex, [Zn2(PhBIMP)­(Cl)­(DMF)]2+ (3), as a control. The binuclear Zn­(II)-thiolate complexes [Zn2(PhBIMP)­(μ-SR)]2+ (R = Ph, 4a; 3-Br-C6H4, 4b) have also been synthesized by avoiding the C–S bond cleavage reaction. Based on the experimental results for the effects of H2O and Et3N on 1, 4a, and 4b, the complex [Zn2(PhBIMP)­(μ-SR)­(OH)]1+ has been proposed to be the active intermediate that precedes the C–S bond cleavage of thiolates. The complex [Zn2(PhBIMP)­(μ-SCOPh)­(DMF)]2+ (5) also demonstrates the hydrolysis of the coordinated thiobenzoate to produce [Zn2(PhBIMP)­(μ-O2CPh)­(MeCN)]2+ (6). However, unlike 4a and 5, the benzeneselenolate-bridged complex, [Zn2(PhBIMP)­(μ-SePh)]2+ (7), does not generate the species, [Zn2(PhBIMP)­(μ-SePh)­(OH)]1+, in solution, and in line with that, the coordinated benzeneselenolate in 7 does not undergo hydrolysis to generate hydroselenide and phenol. Finally, a comparative study for the transfer reactivity of the bridging –SH, –SPh, –SC­(O)­Ph, and –SePh ligands in 2, 4a, 5, and 7, respectively, toward selected organic substrates has been performed to reveal the distinct differences in the reactivity of these bridging ligands.