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The coordination chemistry of solvated metal ions in DMPU

a study of a space-demanding solvent

Lundberg, Daniel (2006). The coordination chemistry of solvated metal ions in DMPU. Diss. (sammanfattning/summary) Uppsala : Sveriges lantbruksuniv., Acta Universitatis agriculturae Sueciae, 1652-6880 ; 2006:23
ISBN 91-576-7072-2
[Doctoral thesis]

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Abstract

This thesis summarizes and discusses the results of several individual studies on the solvation of metal ions in the solvent N,N’-dimethylpropyleneurea, DMPU, including the iron(II), iron(III), zinc(II), cadmium(II), and lanthanoid(III) ions. These studies have shown that the solvation process in DMPU is sometimes very different to those in corresponding aqueous systems. This is due to the the space-demanding properties the DMPU molecule has when coordinating to metal ions, with its two methyl groups close to the coordinating oxygen atom. The methyl groups effectively hinder/hamper the metal ion from reaching the coordination numbers present in hydrate and solvate complexes with solvent molecules with much lower spatial demands. The investigations were performed with different X-ray techniques, including extended X-ray absorption fine structure (EXAFS), large angle X-ray scattering (LAXS), and single crystal X-ray diffraction (XRD) and included both studies in solution (EXAFS and LAXS) and solid state (EXAFS and XRD). A coordination number reduction, compared to the corresponding hydrates, was found in all of the studied systems, except cadmium(II). Furthermore, the coordination number in solution was in several cases not the same as in the respective solid state. In solvents where five-coordinated metal ion solvates are dominating, there is an increase in the ability to form complexes, e.g. fairly strong iron(III) bromide complexes are formed in DMPU. All DMPU solvated lanthanoid(III) ions, except lutetium(III), are seven-coordinated in solution, whereas they are six-coordinated in the solid state, as well as the DMPU solvated lutetium(III) ion in solution. The DMPU solvated zinc(II) and cadmium(II) ions are fourand six-coordinated in the solid state, but both show indications of having a relatively large fraction of transient five-coordinated complexes in solution. This indicates associative and dissociative ligand exchange processes, respectively. The first four-coordinated cadmium(II) iodide with atomic parameters, bis[1,3-dimethyl-3,4,5,6-tetrahydropyrimidin- 2(1H)-one-κO]diiodocadmium(II), has been structurally determined.

Authors/Creators:Lundberg, Daniel
Title:The coordination chemistry of solvated metal ions in DMPU
Subtitle:a study of a space-demanding solvent
Year of publishing :March 2006
Volume:2006:23
Number of Pages:79
Papers/manuscripts:
NumberReferences
ALLI. Lundberg, D. and Eriksson, L., Bis[1,3-dimethyl-3,4,5,6-tetrahydropyrimidin-2(1H)-one-κO]diiodocadmium(II), Acta Crystallographica, E62, 2006, m400-m401. II. Lundberg, D., Eriksson, L, D’Angelo, P. and Persson, I., A structural study of the N,N’-dimethylpropyleneurea solvated zinc(II) and cadmium(II) ions in solution and crystalline state., Accepted for publication Journal of Molecular Liquids III. Lundberg, D., Ullström, A.-S., D’Angelo, P., Warminska, D. and Persson, I., On the structure and complex formation of iron(III) bromide in solution and crystalline state in the space-demanding solvent N,N’-dimethylpropyleneurea. Submitted to Dalton Transactions IV. Lundberg, D., Ullström, A.-S., D’Angelo, P., and Persson, I., A structural study of the hydrated and the dimethylsulfoxide, N,N’-dimethylpropyleneurea, and N,N-dimethylthioformamide solvated iron(II) and iron(III) ions in solution and solid state., Submitted to Inorganica Chimica Acta V. Lundberg, D., D’Angelo, P., De Panfilis, S. and Persson, I., An EXAFS study of N,’N-dimethylpropyleneurea solvated lanthanoid(III) ions in solution and solid state, In manuscript
Place of Publication:Uppsala
ISBN for printed version:91-576-7072-2
ISSN:1652-6880
Language:English
Publication Type:Doctoral thesis
Full Text Status:Public
Agris subject categories.:X Agricola extesions > X50 Chemistry
Subjects:Not in use, please see Agris categories
Agrovoc terms:chemistry, cadmium, iron, ions
Keywords:N, N’-dimethylpropyleneurea (DMPU), cadmium(II), iron(II), iron(III), lanthanoid(III), zinc(II), five-coordination, EXAFS, LAXS, solvation
URN:NBN:urn:nbn:se:slu:epsilon-990
Permanent URL:
http://urn.kb.se/resolve?urn=urn:nbn:se:slu:epsilon-990
ID Code:1072
Department:(NL, NJ) > Dept. of Chemistry (until 131231)
Deposited By: Daniel Lundberg
Deposited On:21 Mar 2006 00:00
Metadata Last Modified:02 Dec 2014 10:09

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