Structural and Electronic Trends for Five Coordinate 1st Row Transition Metal Complexes: Mn(II) to Zn(II) Captured in a Bis(iminopyridine) Framework (original) (raw)

Dalton Trans., 2016

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.

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