Acceptorless Dehydrogenative Cross-Coupling of Primary Alcohols Catalyzed by an N‑Heterocyclic Carbene–Nitrogen–Phosphine Chelated Ruthenium(II) Complex

The acceptorless dehydrogenative cross-coupling of primary alcohols to form cross-esters with the liberation of H₂ gas was enabled using a [RuCl­(η⁶-C₆H₆)­(κ²-CNP)]­[PF₆]Cl complex as the catalyst. This sustainable protocol is applicable to a broad range of primary alcohols, particularly for the sterically demanding ones, featuring good functional group tolerance and high selectivity. The good catalytic performance can be attributed to the nitrogen–phosphine-functionalized N-heterocyclic carbene (CNP) ligand, which adopts a facial coordination mode as well as the facile dissociation of coordinated benzene.