Issue 14, 2016

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

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

Supplementary files

Article information

Article type
Paper
Submitted
24 四月 2015
Accepted
18 六月 2015
First published
01 七月 2015

Dalton Trans., 2016,45, 5989-5998

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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