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Synthesis, structural studies and solubility properties of zinc(II), nickel(II) and copper(II) complexes of bulky tris(triazolyl)borate ligands

Tris(triazolyl)borate (Ttz) ligands are sterically similar to tris(pyrazolyl)borate (Tp) but Ttz complexes show improved solubility in water and alcohols. Bulky tris(triazolyl)borate ligands produce four and five coordinate zinc, copper and nickel complexes for enzyme modeling. This allows for steri...

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Bibliographic Details
Published in:Inorganica Chimica Acta 2010-06, Vol.363 (10), p.2163-2170
Main Authors: Bongiovanni, Jessica L., Rowe, Brittany W., Fadden, Patrick T., Taylor, Michael T., Wells, Kirsten R., Kumar, Mukesh, Papish, Elizabeth T., Yap, Glenn P.A., Zeller, Matthias
Format: Article
Language:English
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Summary:Tris(triazolyl)borate (Ttz) ligands are sterically similar to tris(pyrazolyl)borate (Tp) but Ttz complexes show improved solubility in water and alcohols. Bulky tris(triazolyl)borate ligands produce four and five coordinate zinc, copper and nickel complexes for enzyme modeling. This allows for steric, electronic and solubility comparisons of the Ttz and Tp ligand classes. Tris(triazolyl)borate (Ttz) ligands are sterically similar to tris(pyrazolyl)borate (Tp) but complexes of Ttz show improved solubility in water and alcohols due to their propensity for forming hydrogen bonds. Recently developed bulky tris(triazolyl)borate ligands can produce four and five coordinate transition metal complexes and serve as models for enzyme active sites in an aqueous environment. Herein we report the synthesis of such complexes, i.e. (Ttz t Bu,Me)ZnCl, (Ttz t Bu,Me)ZnBr, (Ttz t Bu,Me)NiCl, and (Ttz t Bu,Me)CuCl, which were analyzed by X-ray crystallographic and spectroscopic methods [Ttz t Bu,Me = tris(3- t-butyl-5-methyl-1,2,4-triazolyl)borate]. (Ttz t Bu,Me)ZnCl crystallizes as two different polymorphs with cubic and monoclinic symmetry. Both polymorphs of (Ttz t Bu,Me)ZnCl and (Ttz t Bu,Me)ZnBr have tetrahedral zinc atoms whereas the geometries at the metal in (Ttz t Bu,Me)NiCl and (Ttz t Bu,Me)CuCl are distorted tetrahedral. All complexes are methanol soluble and they also dissolve in methanol/water mixtures with up to 60% water.
ISSN:0020-1693
1873-3255
DOI:10.1016/j.ica.2010.03.010