Synthesis, characterization, and reactivity of Fe complexes containing cyclic diazadiphosphine ligands: the role of the pendant base in heterolytic cleavage of H2

The iron complexes CpFe(P(Ph)(2)N(Bn)(2))Cl (1-Cl), CpFe(P(Ph)(2)N(Ph)(2))Cl (2-Cl), and CpFe(P(Ph)(2)C(5))Cl (3-Cl)(where P(Ph)(2)N(Bn)(2) is 1,5-dibenzyl-1,5-diaza-3,7-diphenyl-3,7-diphosphacyclooctane, P(Ph)(2)N(Ph)(2) is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane, and P(Ph)(2)C(5) is 1,4-diphenyl-1,4-diphosphacycloheptane) have been synthesized and characterized by NMR spectroscopy, electrochemical studies, and X-ray diffraction. These chloride derivatives are readily converted to the corresponding hydride complexes CpFe(P(Ph)(2)N(Bn)(2))H (1-H), CpFe(P(Ph)(2)N(Ph)(2))H (2-H), CpFe(P(Ph)(2)C(5))H (3-H)] and H(2) complexes CpFe(P(Ph)(2)N(Bn)(2))(H(2))]BAr(F)(4), 1-H(2)]BAr(F)(4), (where BAr(F)(4) is B(3,5-(CF(3))(2)C(6)H(3))(4)](-)), CpFe(P(Ph)(2)N(Ph)(2))(H(2))]BAr(F)(4), 2-H(2)]BAr(F)(4), and CpFe(P(Ph)(2)C(5))(H(2))]BAr(F)(4), 3-H(2)]BAr(F)(4), as well as CpFe(P(Ph)(2)N(Bn)(2))(CO)]BAr(F)(4), 1-CO]Cl. Structural studies are reported for 1-H(2)]BAr(F)(4), 1-H, 2-H, and 1-CO]Cl. The conformations adopted by the chelate rings of the P(Ph)(2)N(Bn)(2) 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]BAr(F)(4) is 2.848 ?, considerably shorter than the sum of the van der Waals radii of N and C atoms. Studies of H/D exchange by the complexes 1-H(2)](+), 2-H(2)](+), and 3-H(2)](+) carried out using H(2) and D(2) indicate that the relatively rapid H/D exchange observed for 1-H(2)](+) and 2-H(2)](+) compared to 3-H(2)](+) is consistent with intramolecular heterolytic cleavage of H(2) mediated by the pendant amine. Computational studies indicate a low barrier for heterolytic cleavage of H(2). These mononuclear Fe(II) 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.