2‐(2′‐Pyridyl)‐4,6‐diphenylphosphinine versus 2‐(2′‐Pyridyl)‐4,6‐diphenylpyridine: Synthesis, Characterization, and Reactivity of Cationic RhIII and IrIII Complexes Based on Aromatic Phosphorus Heterocycles

Abstract

The bidentate P,N hybrid ligand 1 allows access for the first time to novel cationic phosphinine-based Rh(III) and Ir(III) complexes, broadening significantly the scope of low-coordinate aromatic phosphorus heterocycles for potential applications. The coordination chemistry of 1 towards Rh(III) and Ir(III) was investigated and compared with the analogous 2,2'-bipyridine derivative, 2-(2'-pyridyl)-4,6-diphenylpyridine (2), which showed significant differences. The molecular structures of [RhCl(Cp*)(1)]Cl and [IrCl(Cp*)(1)]Cl (Cp*=pentamethylcyclopentadienyl) were determined by means of X-ray diffraction and confirm the mononuclear nature of the λ(3) -phosphinine-Rh(III) and Ir(III) complexes. In contrast, a different reactivity and coordination behavior was found for the nitrogen analogue 2, especially towards Rh(III) as a bimetallic ion pair [RhCl(Cp*)(2)](+) [RhCl3 (Cp*)](-) is formed rather than a mononuclear coordination compound. [RhCl(Cp*)(1)]Cl and [IrCl(Cp*)(1)]Cl react with water regio- and diastereoselectively at the external PC double bond, leading exclusively to the anti-addition products [MCl(Cp*)(1H⋅OH)]Cl as confirmed by X-ray crystal-structure determination.