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Issue 14, 2016
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Synthesis and characterization of bis(imino)pyridine complexes of divalent Mg and Zn

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Abstract

Phenyl-bis(imino)pyridine (PhI2P) complexes, (PhI2P)ZnCl2 (1), (PhI2P)ZnCl (2) and (PhI2P)Zn(py)Cl (3) were obtained with the I2P ligand in both the neutral and the one-electron reduced state. In all examples, the metal ion is Zn(II). Metrical parameters obtained from solid state structures of 2 and 3 indicate that the PhI2P ligand exists as a radical which is supported at the carbon atom of the imino donor, and this electronic state is also apparent in the analogous one-electron reduced ligand Al(III) complex, (PhI2P)AlCl2 (4), that we prepared for comparison. We were unable to obtain PhI2P Mg complexes, and so the more electron rich methyl-substituted bis(imino)pyridine ligand, MeI2P, was investigated. Reaction of two-electron reduced MeI2P with MgCl2 and Mg(OTf)2 did afford the two-electron reduced ligand complexes [(MeI2P2−)Mg(THF)]2(μ-MgCl2) (5) and (MeI2P2−)Mg(THF)2 (6), respectively (MeI2P = 2,6-bis(1-methylethyl)-N-(2-pyridinylmethylene)phenylamine). Complex 5 crystallizes as a trinuclear Mg complex consisting of two (MeI2P2−)Mg moieties bridged by MgCl2 and the (MeI2P2−) ligand is symmetric across the pyridine ring, but is not planar. In contrast, the (MeI2P2−) ligand in 6 is asymmetric across the pyridine ring and all atoms in the ligand are coplanar. Cyclic voltammetry measurements reveal that in complexes, 1, 4, 5, 6, the I2P0, I2P, and I2P2− ligand charge states are accessible electrochemically.

Graphical abstract: Synthesis and characterization of bis(imino)pyridine complexes of divalent Mg and Zn

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Publication details

The article was received on 24 Apr 2015, accepted on 18 Jun 2015 and first published on 01 Jul 2015


Article type: Paper
DOI: 10.1039/C5DT01541C
Citation: Dalton Trans., 2016,45, 5989-5998
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    Synthesis and characterization of bis(imino)pyridine complexes of divalent Mg and Zn

    T. W. Myers, T. J. Sherbow, J. C. Fettinger and L. A. Berben, Dalton Trans., 2016, 45, 5989
    DOI: 10.1039/C5DT01541C

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