title: Synthesis and structural characterization of high spin M/Cu (M = Mn, Fe) heterobimetallic and Fe/Cu2 trimetallic phosphinoamides.
abstract: The heterobimetallic complexes [Mn((i)PrNPPh(2))(3)Cu((i)PrNHPPh(2))] (1) and [Fe((i)PrNPPh(2))(3)Cu((i)PrNHPPh(2))] (2) have been synthesized by the one pot reaction of LiN(i)PrPPh(2), MCl(2) (M = Mn, Fe), and CuI in high yield. Addition of excess CuI into 2 or directly to the reaction mixture led to the formation of a heterotrimetallic [Fe((i)PrNPPh(2))(3)Cu(2)((i)PrNPPh(2))] (3) in good yield. Complexes 1-3 have been characterized by means of elemental analysis, paramagnetic (1)H NMR, UV-vis spectroscopy, cyclic voltammetry, and single crystal X-ray analysis. In all three complexes, Mn or Fe are in the +2 oxidation state and have a high spin electron configuration, as evidenced by solution Evans' method. In addition, the oxidation state of Fe in complex 3 is confirmed by zero-field (57)Fe Mössbauer spectroscopy. X-ray crystallography reveals that the three coordinate Mn/Fe centers in the zwitterionic complexes 1-3 adopt an unusual trigonal planar geometry.
authors.affiliation: Department of Chemistry, Brandeis University, 415 South Street, Waltham, Massachusetts 02454, United States.
authors.forename: Subramaniam
authors.initials: S
authors.lastname: Kuppuswamy
authors.forename: Benjamin G
authors.initials: BG
authors.lastname: Cooper
authors.forename: Mark W
authors.initials: MW
authors.lastname: Bezpalko
authors.forename: Bruce M
authors.initials: BM
authors.lastname: Foxman
authors.forename: Tamara M
authors.initials: TM
authors.lastname: Powers
authors.forename: Christine M
authors.initials: CM
authors.lastname: Thomas