Synthesis, structure, and physical properties for a series of trigonal bipyramidal M(II)-Cl complexes with intramolecular hydrogen bonds.

Dalton Transactions : an International Journal of Inorganic Chemistry
Nathaniel S SickermanA S Borovik

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 [M(II)(TAO)(Cl)](+), where M(II) = 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.

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Citations

Oct 18, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Ellen M MatsonAlison R Fout
Mar 25, 2014·Inorganic Chemistry·Cameron M MooreNathaniel K Szymczak
Aug 12, 2014·Inorganic Chemistry·Johanna M BlacquiereJames M Mayer
May 28, 2016·Chemical Communications : Chem Comm·Matthew D HartleMichael D Pluth
Nov 12, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Travis Marshall-Roth, Seth N Brown
Nov 28, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Maria StrianeseClaudio Pellecchia
Feb 4, 2015·Angewandte Chemie·Dipankar SahooSankar Prasad Rath
Jun 26, 2015·Angewandte Chemie·Dipankar SahooSankar Prasad Rath
Aug 8, 2019·Inorganic Chemistry·Evan J GardnerTimothy H Warren

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