Pyrazole–pyridine–pyrazole (NNN) ruthenium(ii) complex catalyzed acceptorless dehydrogenation of alcohols to aldehydes

Abstract

A new series of cationic ruthenium(II) complexes, [RuCl(PPh₃)₂(κ³-NNN-L1)]Cl (1), [RuH(PPh₃)₂(κ³-NNN-L2)]Cl (2), and [RuH(PPh₃)₂(κ³-NNN-L3)]Cl (3), bearing a 2,6-bis (1-R-5-methyl-pyrazol-3-yl) pyridine ligand (L1: R = H, L2: R = C₆H₄-p-CF₃, L3: R = C₆H₄-p-OCH₃), were synthesized and characterized with NMR, HRMS, and single-crystal X-ray diffraction. Their catalytic application was investigated in the acceptorless dehydrogenation (AD) of primary alcohols. Complex 1 outperformed 2 and 3 in terms of the selectivity towards the aldehydes, and provided the aldehydes with a yield of up to 99%, with good functional group tolerance under mild conditions. In addition, the only by-product of the reaction was dihydrogen, which can be collected as clean energy, and the reaction meets the requirements of environment-friendly chemistry. Complex 1 also proved to be a promising catalyst in the sequential AD/condensation reaction between the primary and secondary alcohols, affording α,β-unsaturated ketones in moderate to good selectivity.