title: Structural and electronic trends for five coordinate 1(st) row transition metal complexes: Mn(ii) to Zn(ii) captured in a bis(iminopyridine) framework.
abstract: The preparation and characterization of a series of divalent 3d transition metal complexes supported by a tridentate planar bis(iminopyridine) ligand are reported. The complexes {2,6-[PhC[double bond, length as m-dash]N(tBu2C6H3)]2C5H3N}MBr2 (M = Mn, Fe, Co, Ni, Cu, Zn), 1-6, were characterized by single crystal X-ray structural studies revealing complexes with pentacoordinate distorted square pyramidal coordination environments. This assembly of complexes provided a unique array for examining the relationship between experimental structure and computed electronic structure. While experimental structural features basically correlated with the Irving-Williams series, some clear deviations were rationalized through the computational analysis. A balance of bis(imino)pyridine/metal with bonding/antibonding π interactions was used to explain the divergent directions of Fe(ii)-N and Co(ii)-N bond lengths. Similarly, orbital details were used to justify the opposing change in Cu-Brap and Cu-Brbas bond lengths. Furthermore, computational analysis provided a unique method to document a surprising low bond order for the M-N bonds of bis(imino)pyridine ligand in this series.
authors.affiliation: Department of Chemistry and Biomolecular Sciences, Center for Catalysis Research and Innovation, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada. darrrin@uottawa.ca.
authors.forename: Titel
authors.initials: T
authors.lastname: Jurca
authors.forename: Sarah
authors.initials: S
authors.lastname: Ouanounou
authors.forename: Wei-Chih
authors.initials: WC
authors.lastname: Shih
authors.forename: Tiow-Gan
authors.initials: TG
authors.lastname: Ong
authors.forename: Glenn P A
authors.initials: GP
authors.lastname: Yap
authors.forename: Ilia
authors.initials: I
authors.lastname: Korobkov
authors.forename: Serge
authors.initials: S
authors.lastname: Gorelsky
authors.forename: Darrin
authors.initials: D
authors.lastname: Richeson