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

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

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

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Fettinger, James C. Berben, Louise A. Myers, Thomas W. Sherbow, Tobias J.
Description	Author Affiliation: Myers TW ( Department of Chemistry, University of California, Davis, California 95616, USA. laberben@ucdavis.edu.); Sherbow TJ ( Department of Chemistry, University of California, Davis, California 95616, USA. laberben@ucdavis.edu.); Fettinger JC ( Department of Chemistry, University of California, Davis, California 95616, USA. laberben@ucdavis.edu.); Berben LA ( Department of Chemistry, University of California, Davis, California 95616, USA. laberben@ucdavis.edu.)
Abstract	Phenyl-bis(imino)pyridine $(^{Ph}I_{2}P)$ complexes, $(^{Ph}I_{2}P)ZnCl_{2}$ (1), $(^{Ph}I_{2}P^{−})ZnCl$ (2) and $(^{Ph}I_{2}P^{−})Zn(py)Cl$ (3) were obtained with the $I_{2}P$ 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 $^{Ph}I_{2}P^{−}$ 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, $(^{Ph}I_{2}P^{−})AlCl_{2}$ (4), that we prepared for comparison. We were unable to obtain $^{Ph}I_{2}P$ Mg complexes, and so the more electron rich methyl-substituted bis(imino)pyridine ligand, $^{Me}I_{2}P,$ was investigated. Reaction of two-electron reduced $^{Me}I_{2}P$ with $MgCl_{2}$ and $Mg(OTf)_{2}$ did afford the two-electron reduced ligand complexes $[(^{Me}I_{2}P^{2−})Mg(THF)]_{2}(μ-MgCl_{2})$ (5) and $(^{Me}I_{2}P^{2−})Mg(THF)_{2}$ (6), respectively $(^{Me}I_{2}P$ = 2,6-bis(1-methylethyl)-N-(2-pyridinylmethylene)phenylamine). Complex 5 crystallizes as a trinuclear Mg complex consisting of two $(^{Me}I_{2}P^{2−})Mg$ moieties bridged by $MgCl_{2}$ and the $(^{Me}I_{2}P^{2−})$ ligand is symmetric across the pyridine ring, but is not planar. In contrast, the $(^{Me}I_{2}P^{2−})$ 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 $I_{2}P^{0},$ $I_{2}P^{−},$ and $I_{2}P^{2−}$ ligand charge states are accessible electrochemically.
ISSN	14779226
Issue Number	14
Journal	Dalton Trans.
Volume Number	45
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2016-04-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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