Zirconium complexes of amino(polyphenolic) ligands and their hydrolytic stability |
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| Affiliation: | 1. School of Chemistry, The University of Edinburgh, Joseph Black Building, Kings Buildings, West Mains Road, Edinburgh EH9 3JJ, UK;2. Nuclear Materials Authority (NMA), P.O. Box 530, Almaadi, Cairo, Egypt;1. Department of Biology, Biotechnical Faculty, University of Ljubljana, Večna pot 111, SI-1000, Ljubljana, Slovenia;2. Department of Analytical Chemistry, National Institute of Chemistry, Hajdrihova 19, SI-1000, Ljubljana, Slovenia;1. CEITEC IPM, Institute of Physics of Materials, v.v.i., Academy of Sciences of the Czech Republic, Brno, Czech Republic;2. Institute of Rock Structure and Mechanics, v.v.i., Academy of Sciences of the Czech Republic, Prague, Czech Republic;3. Institute of Macromolecular Chemistry, v.v.i., Academy of Sciences of the Czech Republic, Prague, Czech Republic;4. Institute of Materials Science and Engineering, Faculty of Mechanical Engineering, Brno University of Technology, Brno, Czech Republic;5. Institute of Physics of Materials, v.v.i., Academy of Sciences of the Czech Republic, Brno, Czech Republic;1. Department of Chemistry, Indian Institute of Technology Kanpur, 208016, India;2. Department of Mechanical Engineering, Indian Institute of Technology Kanpur, 208016, India;1. Dipartimento di Ingegneria dell’Impresa, Università degli Studi di Roma Tor Vergata, Via del Politecnico 1, 00133 Roma, Italy;2. Dipartimento di Ingegneria Meccanica ed Aerospaziale, Università degli Studi di Roma La Sapienza, Via Eudossiana 18, 00184 Roma, Italy |
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| Abstract: | Three amino(polyphenolic) ligands, N,N′-bis(5-tert-butyl-2-hydroxybenzyl)-1,2-diaminoethane 1, tris(5-tert-butyl-2-hydroxy-3-methylbenzyl)amine 3, its 3-chloro analogue 4 and their ZrIV complexes have been synthesised. The crystal structure of the ZrIV complex of tris(5-tert-butyl-3-chloro-2-hydroxybenzyl)amine, shows this to be [Zr(4-2H)2] in which both ligands exists in a zwitterionic form with one alkylammonium and three phenolate groups. The complexes are stable in a two phase, chloroform/water, system at high pH, but the zirconium is stripped at pH < 2.5. The pH value needed to strip 50% of the ZrIV from the complex [Zr(1-4H)] of the tetraphenolic ligand is ∼2.0 whilst the complexes [Zr(3-2H)2] and [Zr(4-2H)2] of the triphenolic ligands are slightly more stable with pH1/2 values of ∼1.4. We were unable to use the ligands to extract zirconium from low pH aqueous zirconium oxychloride solutions into an organic phase under a variety of conditions. |
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