Bajnóczi, Éva G. and Pálinkó, István and Körtvélyesi, Tamás and Bálint, Szabolcs and Bakó, Imre and Sipos, Pál and Persson, Ingmar
(2014).
Speciation and the structure of lead(II) in hyperalkaline aqueous solution.
Dalton Transactions: an international journal of inorganic chemistry [incorporating Acta Chemica Scandinavica]. 43
, 17971 - 17979
[Research article]
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Official URL: http://dx.doi.org/10.1039/c4dt02757d
Abstract
The identity of the predominating lead(II) species in hyper-alkaline aqueous solution has been determined by Raman spectroscopy, and ab initio quantum chemical calculations and its structure has been determined by EXAFS. The observed and calculated Raman spectra for the [Pb(OH)(3)](-) complex are in agreement while they are different for two-coordinated complexes and complexes containing Pb=O double bonds. 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 lead(II) and tin(II) in hyper-alkaline aqueous solutions suggest that the last stepwise hydroxido complex of lead(II) is [Pb(OH)(3)](-). The Pb-O bond distance in the [Pb(OH)(3)](-) complex as determined is remarkably short, 2.216 angstrom, and has low symmetry as no multiple back-scattering is observed. The [Pb(OH)(3)](-) complex has most likely trigonal pyramidal geometry as all reported three-coordinated lead(II) complexes in the solid state. From single crystal X-ray data, the bond lengths for O-coordinated lead(II) complexes with low coordination numbers are spread over an unusually wide interval, 2.216-2.464 angstrom for N = 3. The Pb-O bond distance is at the short side and within the range of three coordinated complexes, as also observed for the trihydroxidostannate(II) complex indicating that the hydroxide ion forms short bonds with d(10)s(2) metal ions with occupied anti-bonding orbitals.
Authors/Creators: | Bajnóczi, Éva G. and Pálinkó, István and Körtvélyesi, Tamás and Bálint, Szabolcs and Bakó, Imre and Sipos, Pál and Persson, Ingmar | ||||||
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Title: | Speciation and the structure of lead(II) in hyperalkaline aqueous solution | ||||||
Series Name/Journal: | Dalton Transactions: an international journal of inorganic chemistry [incorporating Acta Chemica Scandinavica] | ||||||
Year of publishing : | 2014 | ||||||
Depositing date: | 10 February 2015 | ||||||
Volume: | 43 | ||||||
Page range: | 17971 - 17979 | ||||||
Number of Pages: | 5 | ||||||
Publisher: | Royal Society of Chemistry | ||||||
ISSN: | 1477-9226 | ||||||
Language: | English | ||||||
Publication Type: | Research article | ||||||
Refereed: | Yes | ||||||
Article category: | Scientific peer reviewed | ||||||
Version: | Accepted version | ||||||
Full Text Status: | Public | ||||||
Agris subject categories.: | X Agricola extesions > X50 Chemistry | ||||||
Subjects: | (A) Swedish standard research categories 2011 > 1 Natural sciences > 104 Chemical Sciences > Inorganic Chemistry | ||||||
Agrovoc terms: | chemistry, calculation, potentiometry, solutions, chemicophysical properties | ||||||
Keywords: | hyper-alkaline aqueous solution, lead(II), speciation, structure, tin(II)-hydroxid complex, potentiometric titrations, spectoscopy, quantum chemical calculations, thermodynamic studies | ||||||
URN:NBN: | urn:nbn:se:slu:epsilon-e-2392 | ||||||
Permanent URL: | http://urn.kb.se/resolve?urn=urn:nbn:se:slu:epsilon-e-2392 | ||||||
Additional ID: |
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ID Code: | 11768 | ||||||
Faculty: | NJ - Fakulteten för naturresurser och jordbruksvetenskap | ||||||
Department: | (NL, NJ) > Department of Chemistry and Biotechnology (140101-161231) | ||||||
Deposited By: | SLUpub Connector | ||||||
Deposited On: | 10 Feb 2015 11:28 | ||||||
Metadata Last Modified: | 09 Sep 2020 14:17 |
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