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Issue 15, 2012
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Synthesis, structure, and physical properties for a series of trigonal bipyramidal MII–Cl complexes with intramolecular hydrogen bonds

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Abstract

A series of transition metal chloro complexes with the tetradentate tripodal tris(2-amino-oxazoline)amine ligand (TAO) have been synthesized and characterized. X-Ray structural analyses of these compounds demonstrate the formation of the mononuclear complexes [MII(TAO)(Cl)]+, where MII = Cr, Mn, Fe, Co, Ni, Cu and Zn. These complexes exhibit distorted trigonal-bipyramidal geometry, coordinating the metal through an apical tertiary amine, three equatorial imino nitrogen atoms, and an axial chloride anion. All the complexes possess an intramolecular hydrogen-bonding (H-bonding) network within the cavity occupied by the metal-bound chloride ion. The metal–chloride bond distances are atypically long, which is attributed to the effects of the H-bonding network. Nuclear magnetic resonance (NMR) spectroscopy of the Zn complex suggests that the solid-state structures are representative of that observed in solution, and that the H-bonding interactions persist as well. Additionally, density functional theory (DFT) calculations were carried out to probe the electronic structures of the complexes.

Graphical abstract: Synthesis, structure, and physical properties for a series of trigonal bipyramidal MII–Cl complexes with intramolecular hydrogen bonds

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Article information


Submitted
23 Nov 2011
Accepted
21 Dec 2011
First published
15 Feb 2012

Dalton Trans., 2012,41, 4358-4364
Article type
Paper

Synthesis, structure, and physical properties for a series of trigonal bipyramidal MII–Cl complexes with intramolecular hydrogen bonds

N. S. Sickerman, Y. J. Park, G. K.-Y. Ng, J. E. Bates, M. Hilkert, J. W. Ziller, F. Furche and A. S. Borovik, Dalton Trans., 2012, 41, 4358
DOI: 10.1039/C2DT12244H

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