The Structure of Pb(II) Ion in Hyper-Alkaline Aqueous Solution

Bajnóczi, Éva G. and Pálinkó, István and Bálint, Szabolcs and Bakó, Imre and Sipos, Pál and Perssone, Ingmar (2014) The Structure of Pb(II) Ion in Hyper-Alkaline Aqueous Solution. DALTON TRANSACTIONS, 43 (46). pp. 17539-17543. ISSN 1477-9226

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Abstract

The structure of lead(II) in hyper-alkaline aqueous solutions has 5 been determined by EXAFS and Raman spectroscopy, and from ab initio quantum chemical calculations. The formation of a single species was observed, in which the Pb-O bond distance is remarkably short, 2.216 Å, and the complex is non-linear. From single crystal X-ray data, the bond lengths for O-coordinated 10 lead(II) complexes with low coordination numbers are spread over an unusually wide interval (e.g., 2.216 – 2.464 Å for N = 3). The Pb-O bond distance is within the range of three coordinated complexes (i.e., [Pb(OH)3]− or [PbO(OH)2]2−) but the possibility of the two coordinated [PbO(OH)]− complex has also been 15 considered. The observed Raman spectrum and that calculated for [Pb(OH)3]− show obvious similarity. Predicted bond lengths are also consistent with the presence of [Pb(OH)3]– and exclude the formation of Pb=O double bond(s). These observations together with experimentally established analogies between Pb(II) and 20 Sn(II) in hyper-alkaline solutions suggest, that the last stepwise hydroxido complex of both tin(II) and lead(II) is [M(OH)3]−. The structure of the complexes is trigonal pyramid.

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