An NNN Pd(ii) pincer complex with 1,1-diaminoazine: a versatile catalyst for acceptorless dehydrogenative coupling reactions

Abstract

An azine-based, non-palindromic, neutral NNN-pincer ligand was synthesised in a single step with an yield of 85%. The palladation of the ligand, using Pd(OAc)₂, was performed in acetonitrile at room temperature to obtain the pincer complex in 88% yield through a simple, cost-effective, and straightforward synthetic procedure. The structure of the complex was confirmed by ¹H NMR, ¹³C NMR, FT-IR, and mass spectrometry. The variable temperature NMR spectra revealed the stability of the complex even at higher temperatures, a characteristic feature of pincer complexes. The generated complex proved to be a versatile catalyst for Acceptorless Dehydrogenative Coupling (ADC) to synthesize N-heterocycles: (i) 1,2-disubstituted benzimidazoles, (ii) 2-phenylquinolines, (iii) 2-phenylquinoxalines and (iv) 2-phenylquinazolinones. Since the side products of the reactions are H₂O and H₂ gas, the catalysis can be considered as a green catalytic process. Quantum chemical calculations indicated the participation of a possible nitrene–imide conversion process during the Metal–Ligand Cooperation (MLC) in ADC reactions.