Abstract
Computational studies were undertaken for a series of Cr−M complexes (M = Cu, Rh, Ir) to further explore structural and electronic trends previously observed within Cr−M complexes. The distinct geometric differences in these complexes from the last set of Cr−M complexes studied by our group were reflected in the relative molecular orbital energies of [(η2-XylNPiPr2)Cr(μ-XylNPiPr2)2CuI], [ClCr(μ-iPrNPiPr2)2Rh(η2-iPrNPiPr2)], and [ClCr(μ-iPrNPiPr2)2Ir(η2-iPrNPiPr2)]. σ bonding and antibonding interactions were observed in all three complexes, though the frontier molecular orbitals were primarily nonbonding interactions.\r The synthesis and characterization of the homobimetallic phosphinoamide-linked complex [Fe(MesNPiPr2)3FeCl] was revisited in an attempt to identify the side product formed during the synthesis of [Fe(MesNPiPr2)3FeCl] and to investigate the redox properties and reactivity of [Fe(MesNPiPr2)3FeCl]. The one-electron reduced complex was synthesized by reduction with potassium graphite (KC8).