Carboxylate Bridged Binuclear Cobalt(II) Complexes Catalyze the Hydrolysis of Thiolates to Alcohols

Abstract

A binuclear Co(II) complex, [Co2(PhBIMP)(μ‐O2CPh)(MeCN)]2+ (1) ((PhBIMP is the anion of 2,6 bis[(bis((N‐1‐methyl‐4,5‐diphenylimidazoylmethyl) amino)methyl]‐4‐methylphenol)) catalyzes the hydrolysis of thiolates to the corresponding alcohols/phenols at room temperature. Hydrolysis of 11 different thiolates has been investigated with a catalyst loading of 4 ‐ 6.7 mol% and with the highest TON values reaching 22. Furthermore, the effects of electron donating and electron withdrawing groups on the bridging benzoate of 1 have been investigated. The intermediates, products, and fate of the catalyst have been identified by mass spectrometric, gas chromatographic and gravimetric methods, and based on that, a mechanism for the catalytic cycle has been proposed.