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 ca

SUBMITTER: Oldenhof S 

PROVIDER: S-EPMC5811074 | biostudies-literature | 2015 Feb

REPOSITORIES: biostudies-literature