Synchronous Proton‐Hydride Transfer by a Pyrazole‐Functionalized Protic Mn(I) Complex in Catalytic Alcohol Dehydrogenative Coupling

Abstract

A series of Mn(I) complexes Mn(L1)(CO)3Br, Mn(L2)(CO)3Br, Mn(L1)(CO)3(OAc) and Mn(L3)(CO)3Br [L1 = 2‐(5‐tert‐butyl‐1H‐pyrazol‐3‐yl)‐1,8‐naphthyridine, L2 = 2‐(5‐tert‐butyl‐1H‐pyrazol‐3‐yl)pyridine, L3 = 2‐(5‐tert‐butyl‐1‐methyl‐1H‐pyrazol‐3‐yl)‐1,8‐naphthyridine] were synthesized and fully characterized. The acid‐base equilibrium between the pyrazole and the pyrazolato forms of Mn(L1)(CO)3Br was studied by 1H NMR and UV‐vis spectra. These complexes are screened as catalysts for acceptorless dehydrogenative coupling (ADC) of primary alcohols and aromatic diamines for the synthesis of benzimidazole and quinoline derivatives with the release of H2 and H2O as byproducts. The protic complex Mn(L1)(CO)3Br shows the highest catalytic activity for the synthesis of 2‐substituted benzimidazole derivatives with broad substrate scope, whereas a related complex [Mn(L3)(CO)3Br], which is devoid of the proton responsive β‐NH unit, shows significantly reduced catalytic efficiency validating the crucial role of the β‐NH functionality for the alcohol dehydrogenation reactions. Control experiments, kinetic and deuterated studies, and density functional theory (DFT) calculations reveal a synchronous hydride‐proton transfer by the metal‐ligand construct in the alcohol dehydrogenation step.