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

• Published in: European journal of inorganic chemistry 2024-06, Vol.27 (18), p.n/a
• Main Authors: Chakraborty, Anuj Baran, Ganguly, Tuhin, Bera, Abhijit, Majumdar, Amit
• Format: Article
• Language: English
• Subjects: Alcohols; Benzoates; Catalysis; Catalysts; Cobalt compounds; C−S Bond Cleavage; Dicobalt(II); Gas chromatography; Hydrolysis; Phenols; Room temperature; Spectrometry; Thiolates
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.202400105

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. A benzoate bridged binuclear cobalt(II) complex catalyzes the hydrolysis of aliphatic / aromatic thiolates to the corresponding alcohols / phenols with 4–6.7 mol% catalyst loading and a highest TON of 22 at ambient conditions. The effect of electron donating and electron withdrawing groups on the bridging benzoate is investigated and a mechanism for the catalytic cycle is proposed.