Pyridine versus acetonitrile coordination in rhodium–N-heterocyclic carbene square-planar complexes

Abstract

Experimental and theoretical studies on the factors that control the coordination chemistry of N-donor ligands in square-planar complexes of the type RhCl(NHC)L¹L² (NHC = N-heterocyclic carbene) are presented. The dinuclear complexes [Rh(μ-Cl)(IPr)(η²-olefin)]₂ {IPr = 1,3-bis-(2,6-diisopropylphenyl)imidazol-2-carbene} have been reacted with different combinations of ligands including pyridine, acetonitrile, 2-pyridylacetonitrile, triphenylphosphine, tricyclohexylphosphine, carbon monoxide or molecular oxygen. In addition, the reactivity of RhCl(IPr)(PPh₃)₂ has also been studied. Pyridine preferentially coordinates trans to the carbene ligand whereas π-acceptor ligands (olefin, CO or PPh₃) are prone to bind cis to IPr and trans to chlorido, unless steric bulk hinders the coordination of the ligand (PCy₃). In contrast, acetonitrile is more labile than pyridine but is able to form complexes coordinated cis-to-IPr. Molecular dioxygen also displaces the labile cyclooctene ligand in RhCl(IPr)(η²-coe)(py) to give a square-planar dioxygen adduct which can be transformed into a peroxo derivative by additional coordination of pyridine. Charge decomposition analysis (CDA) shows that σ-donation values are similar for coordination at cis- or trans-IPr positions, whereas efficient π-backbonding is significantly observed at cis position being the favoured coordination site for π-acceptor ligands. The Rh-IPr rotational barrier in a series of square-planar complexes has been analysed. It has been found that the main contribution is the steric hindrance of the ancillary ligand. The presence of a π-donor ligand such as chlorido slows down the dynamic process.