Photochemically induced cyclometalations at simple platinum(II) precursors

Abstract

Photochemical cycloplatinations of 2-arylpyridines and related C∧N ligands, as well as terdentate heteroaromatic N∧N∧C, N∧C∧N, and N∧C∧C compounds, are demonstrated using (Bu4N)2[Pt2Cl6] or [PtCl2(NCPh)2] as precursors at room temperature. Mono- or bis-cyclometalated Pt(II) complexes with C∧N ligands are obtained depending on excitation wavelength and precursor. Monitoring experiments show that photoexcitation enables both the N-coordination and the subsequent C–H metalation. Photochemical synthetic protocols have been developed, which are advantageous with respect to the established thermal procedures and have allowed the synthesis of the first Pt(II) complexes with N∧C∧C ligands.