GRAPHICAL ABSTRACT
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Abstract
Coordination chemical studies of 1H-1,3-benzazaphospholes, π-excess aromatic σ2P-ligands, demonstrate similar ligand properties to those of phosphabenzenes toward MVI(CO)n but marked differences toward nonzerovalent transition metals. Benzazaphosphole d8-metal halide complexes are more strongly destabilized and undergo consecutive reactions, whereas benzazaphosphole coinage metal halide and HgCl2 complexes generally display μ2P- and/or bent η1P-coordination with π-P donor bond contribution, contrasting with the preference of phosphinine CuX complexes for η1P-coordination within the ring plane.