Dehydrogenation of formic acid by Ir–bisMETAMORPhos complexes: experimental and computational insight into the role of a cooperative ligand

Abstract

The synthesis and tautomeric nature of three xanthene-based bisMETAMORPhos ligands (La–Lc) is reported. Coordination of these bis(sulfonamidophosphines) to Ir(acac)(cod) initially leads to the formation of Ir^I(L^H) species (1a), which convert via formal oxidative addition of the ligand to Ir^III(L) monohydride complexes 2a–c. The rate for this step strongly depends on the ligand employed. Ir^III complexes 2a–c were applied in the base-free dehydrogenation of formic acid, reaching turnover frequencies of 3090, 877 and 1791 h⁻¹, respectively. The dual role of the ligand in the mechanism of the dehydrogenation reaction was studied by ¹H and ³¹P NMR spectroscopy and DFT calculations. Besides functioning as an internal base, bisMETAMORPhos also assists in the pre-assembly of formic acid within the Ir-coordination sphere and aids in stabilizing the rate-determining transition state through hydrogen-bonding.