Π-Rich σ²P-Ligands: Unusual Coordination Behavior of 1H-1,3-Benzazaphospholes Toward Late Transition Metals

GRAPHICAL ABSTRACT

Abstract

Coordination chemical studies of 1H-1,3-benzazaphospholes, π-excess aromatic σ²P-ligands, demonstrate similar ligand properties to those of phosphabenzenes toward M^VI(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.

Keywords:

• Phosphorus heterocycles
• P ligands
• coordination modes
• silver complexes
• copper clusters
• mercury
• gold