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Issue 36, 2016
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Structural and electronic trends for five coordinate 1st row transition metal complexes: Mn(II) to Zn(II) captured in a bis(iminopyridine) framework

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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.

Graphical abstract: Structural and electronic trends for five coordinate 1st row transition metal complexes: Mn(ii) to Zn(ii) captured in a bis(iminopyridine) framework

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Publication details

The article was received on 29 Jun 2016, accepted on 06 Aug 2016 and first published on 08 Aug 2016


Article type: Paper
DOI: 10.1039/C6DT02598F
Citation: Dalton Trans., 2016,45, 14327-14334
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    Structural and electronic trends for five coordinate 1st row transition metal complexes: Mn(II) to Zn(II) captured in a bis(iminopyridine) framework

    T. Jurca, S. Ouanounou, W. Shih, T. Ong, G. P. A. Yap, I. Korobkov, S. Gorelsky and D. Richeson, Dalton Trans., 2016, 45, 14327
    DOI: 10.1039/C6DT02598F

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