Change search
ReferencesLink to record
Permanent link

Direct link
Coordination Chemistry Study of Hydrated and Solvated Lead(II) Ions in Solution and Solid State
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Show others and affiliations
2011 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 50, no 3, 1058-1072 p.Article in journal (Refereed) Published
Abstract [en]

The coordination chemistry of lead(II) in the oxygen donor solvents water, dimethylsulfoxide (dmso, Me(2)SO), N,N-dimethylformamide (dmf), N,N-dimethylacetamide (dma), N,N'-dimethylpropyleneurea (dmpu), and 1,1,3,3-tetramethylurea (tmu), as well as in the sulfur donor solvent N,N-dimethylthioformamide (dmtf), has been investigated by extended X-ray absorption fine structure (EXAFS) and/or large angle X-ray scattering (LAXS) in solution, and by single crystal X-ray diffraction and/or EXAFS of solid hydrates and solvates. Lead(II) may either form hemidirected complexes with large bond distance distribution and an apparent gap for excess electron density, or holodirected ones with a symmetric coordination sphere with normal bond distance distribution, depending on the strength of antibonding lead 6s/ligand np molecular orbital interactions and ligand-ligand interactions. The crystallographic data show that the solid lead(II) perchlorate and trifluoromethanesulfonate hydrate structures are hemidirected, while the solid lead(II) solvates of dma and dmpu have regular octahedral configuration with holodirected geometry and mean Pb-O bond distances in the range 2.50-2.52 A. EXAFS data on the hydrated lead(II) ion in aqueous solution show broad bond distance distribution and a lack of inner-core multiple scattering contributions strongly indicating a hemidirected structure. The Pb-O bond distances found both by EXAFS and LAXS, 2.54(1) angstrom, point to a six-coordinate hydrated lead(II) ion in hemidirected fashion with an unevenly distributed electron density. The results obtained for the dmso solvated lead(II) ion in solution are ambiguous, but for the most part support a six-coordinate hemidirected complex. The mean Pb-O bond distances determined in dmf and dma solution by LAXS, 2.55(1) and 2.48(1) angstrom, respectively, indicate that in both solvate complexes lead(II) binds six solvent molecules with the former complex being hemidirected whereas the latter is holodirected. The dmpu and tmu solvated lead(II) ions have a regular holodirected octahedral configuration, as expected given their space-demanding characteristics and ligand-ligand intermolecular interactions. The dmtf solvated lead(II) ion in solution is most likely five-coordinate in a hemidirected configuration, with a mean Pb-S bond distance of 2.908(4) angstrom. New and improved ionic radii for the lead(II) ion in 4-8-coordination in hemi and holodirected configurations are proposed using crystallographic data.

Place, publisher, year, edition, pages
2011. Vol. 50, no 3, 1058-1072 p.
National Category
Materials Chemistry
URN: urn:nbn:se:su:diva-67501DOI: 10.1021/ic1017714ISI: 000286688700046OAI: diva2:470469
authorCount :5Available from: 2011-12-29 Created: 2011-12-28 Last updated: 2011-12-29Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Eriksson, Lars
By organisation
Department of Materials and Environmental Chemistry (MMK)
In the same journal
Inorganic Chemistry
Materials Chemistry

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 222 hits
ReferencesLink to record
Permanent link

Direct link