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 | ||||
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Title: | The coordination chemistry of solvated metal ions in DMPU | ||||
Subtitle: | a study of a space-demanding solvent | ||||
Series Name/Journal: | Acta Universitatis Agriculturae Sueciae | ||||
Year of publishing : | March 2006 | ||||
Number: | 2006:23 | ||||
Number of Pages: | 79 | ||||
Papers/manuscripts: |
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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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