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., 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, [Co 2 (PhBIMP)(μ 2 -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, [Co 2 (PhBIMP)(μ 2 -SH)(RS)(H 2 O)] 1+ ( 2 ), which, in turn, releases the alcohol/phenol (ROH), hydrosulfide (HS - ), and regenerates 1 .