Rhodium(III) and Iridium(III) Complexes of a NHC-Based Macrocycle: Persistent Weak Agostic Interactions and Reactions with Dihydrogen

The synthesis and characterization of five-coordinate rhodium­(III) and iridium­(III) 2,2′-biphenyl complexes [M­(CNC-12)­(biph)]­[BArF4] (M = Rh (1a), Ir (1b)), featuring the macrocyclic lutidine- and NHC-based pincer ligand CNC-12 are reported. In the solid state these complexes are notable for the adoption of weak ε-agostic interactions that are characterized by M···H–C contacts of ca. 3.0 Å by X-ray crystallography and ν­(CH) bands of reduced wavenumber by ATR IR spectroscopy. Remarkably, these interactions persist on dissolution and were observed at room temperature using NMR spectroscopy (CD2Cl2) and solution-phase IR spectroscopy (CCl4). The associated metrics point toward a stronger M···H–C interaction in the iridium congener, and this conclusion is borne out on interrogation of 1 in silico using DFT-based NBO and QTAIM analyses. Reaction of 1 with dihydrogen resulted in hydrogenolysis of the biaryl and formation of fluxional hydride complexes, whose ground state formulations as [Rh­(CNC-12)­H2]­[BArF4] (2a″) and [Ir­(CNC-12)­H2(H2)]­[BArF4] (2b‴) are proposed on the basis of inversion recovery and variable-temperature NMR experiments, alongside a computational analysis. Reactions of 1 and 2 with carbon monoxide help support their respective structural properties.