Can P–H σ-bond complexes be prepared? A computational study by DFT and AIM methods

Abstract

A series of complexes of general formula [CpMn(CO)₂(η²-HPR¹R²·BCl₃)] has been studied by DFT calculations and topological analyses of the charge density thus derived. The 21 complexes included in this study exhibit closely similar Mn–H–P geometries, in spite of a wide range of substituents (R¹; R²) at the phosphorus atom. Topological analysis of the electron density suggests that these are genuine σ-bond complexes, albeit at a later stage on the oxidative addition reaction coordinate than corresponding silanes, with strong Mn–P and Mn–H bonding and a weak P–H interaction.