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

Organometallics 2018 November 13
The synthesis and characterization of five-coordinate rhodium(III) and iridium(III) 2,2'-biphenyl complexes [M(CNC-12)(biph)][BArF 4 ] (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 (CD2 Cl2 ) 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 ][BArF 4 ] ( 2a″ ) and [Ir(CNC-12)H2 (H2 )][BArF 4 ] ( 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.

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