PNNL

Abstract

The iron complexes CpFe(PPh2NBn2)Cl (1-Cl), CpFe(PPh2NPh2)Cl (2-Cl), CpFe(PPh2C5)Cl (3-Cl) (where PPh2NBn2 is 1,5-dibenzyl-1,5-diaza-3,7-diphenyl-3,7-diphosphacyclooctane, PPh2NPh2 is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane, and PPh2C5 is 1,4-diphenyl-1,4-diphosphacycloheptane) have been synthesized and characterized by NMR spectroscopy, electrochemical studies, and X-ray diffraction studies. These chloride derivatives are readily converted to the corresponding hydride complexes CpFe(PPh2NBn2)H (1-H), CpFe(PPh2NPh2)H (2-H), CpFe(PPh2C5)H (3-H)] and H2 complexes [CpFe(PPh2NBn2)(H2)]BArF4, [1-H2]BArF4, (where BArF4 is B[(3,5-(CF3)2C6H3)4]-), [CpFe(PPh2NPh2)(H2)]BArF4, [2-H2]BArF4, and [CpFe(PPh2C5)(H2)]BArF4, [3-H2]BArF4 as well as [CpFe(PPh2NBn2)(CO)]BArF4, [1-CO]BArF4. Structural studies are reported for [1-H2]BArF4, 1-H, 2-H, and [1-CO]BArF4. The conformations adopted by the chelate rings of the PPh2NBn2 ligand in the different complexes are determined by attractive or repulsive interactions between the sixth ligand of these pseudo-octahedral complexes and the pendant N atom of the ring adjacent to the sixth ligand. An example of an attractive interaction is the observation that the distance between the N atom of the pendant amine and the C atom of the coordinated CO ligand for [1-CO]BArF4 is 2.848 Å, considerably shorter than the sum of the van der Waals radii of N and C atoms. Experimental and theoretical studies of H/D exchange by the complexes [1-H2]+, [2-H2]+, and [3-H2]+ indicate that the relatively rapid exchange observed for [1-H2]+ and [2-H2]+ compared to [3-H2]+ is consistent with intramolecular heterolytic cleavage of H2 mediated by the pendant amine. These mononuclear FeII dihydrogen complexes containing pendant amines in the ligands mimic crucial features of the distal Fe site of the active site of the [FeFe] hydrogenase required for H-H bond formation and cleavage. We thank the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences, for support of this research. S.C. (DFT computations) and M. J. O. (NMR experiments) were supported by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under FWP 56073. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.