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Coordination chemistry in liquid ammonia and phosphorous donor solvents

Nilsson, Kersti B. (2005). Coordination chemistry in liquid ammonia and phosphorous donor solvents. Diss. (sammanfattning/summary) Uppsala : Sveriges lantbruksuniv., Acta Universitatis agriculturae Sueciae, 1652-6880 ; 2005:21
ISBN 91-576-7020-x
[Doctoral thesis]

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Abstract

The thesis summarizes and discusses the results from coordination chemistry studies of solvated d10 metal and copper(II) ions, and mercury(II) halide complexes in the strong electron-pair donor solvents liquid and aqueous ammonia, trialkyl phosphite, triphenyl phosphite and trialkylphosphine. The main techniques used are EXAFS, metal NMR and vibrational spectroscopy, and crystallography. Four crystal structures containing ammonia solvated metal ions have been determined. Questions addressed concern whether any changes in the preferential coordination numbers and geometries occur when these metal ions are transferred from aqueous ammonia to liquid ammonia solution, or to phosphorous donor solvents. Liquid ammonia and trialkyl phosphites are found to possess similar electron-pair donor properties, DS=56 for both, while trialkylphosphines are known to be even stronger electron-pair donors. The studies reveal that the ammonia-solvated d10 metal ions obtain very different configurations in liquid ammonia, with gold(I) being linear, copper(I) and silver(I) trigonal, zinc(II) and mercury(II) tetrahedral, and cadmium(II), indium(III) and thallium(III) octahedral. The ammonia-solvated copper(I) and silver(I) ions are linear in aqueous ammonia solution because of the lower ammonia activity, as the third ammine complexes are very weak in aqueous systems. In the phosphorous donor solvents surveyed, the copper(I) ion is tetrahedral while the silver(I) ion is tetrahedral or trigonal and the gold(I) ion is trigonal or linear. The ammonia solvated copper(II) ion has a Jahn-Teller distorted octahedral configuration in liquid ammonia solution and solid [Cu(NH3)6](ClO4)2, as determined by EXAFS. In liquid ammonia, mercury(II) chloride and mercury(II) bromide are completely dissociated, whereas the ammonia solvated mercury(II) iodide, [HgI2(NH3)2], complex has a near tetrahedral configuration. In tri-n-butylphosphine, mercury(II) iodide is completely dissociated, forming a linear solvate complex in a melt at elevated temperature.

Authors/Creators:Nilsson, Kersti B.
Title:Coordination chemistry in liquid ammonia and phosphorous donor solvents
Year of publishing :2005
Volume:2005:21
Number of Pages:50
Papers/manuscripts:
NumberReferences
ALLI. Nilsson K. B & Persson I, The coordination chemistry of copper(I) in liquid ammonia, trialkyl and triphenyl phosphite, and tri-n-butylphosphine solution. 2004, Dalton Transactions, 1312-1319. II. Nilsson K. B., Persson I. & Kessler V.G. The coordination chemistry of the solvated silver(I) and gold(I) ions in aqueous, dimethylsulfoxide, liquid and aqueous ammonia, trialkyl and triphenyl phosphite and tri-n-butylphosphine solution. Submitted to Dalton Transactions. III. Nilsson K. B., Persson I. & Kessler V.G. The coordination chemistry of the copper(II), zinc(II) and cadmium(II) ions in aqueous and liquid ammonia solution, and the crystal structures of hexaamminecopper(II) perchlorate and hexaamminecadmium chloride. Submitted to Dalton Transactions. IV. Nilsson K. B., Maliarik M., Persson I., Fischer A., Ullström A.-S., Eriksson L., & Sandström M. The coordination chemistry of mercury(II) in aqueous and liquid ammonia solution, and the structure of tetraamminemercury(II) perchlorate in solid state. Submitted to Dalton Transactions. V. Nilsson K. B., Maliarik M., Persson I., & Sandström M. Structure and solvation of mercury(II) halides in liquid ammonia, tri-n-butyl phosphite and tri-n-butylphosphine solution. (Manuscript) VI. Nilsson K. B., Persson I. & Maliarik M. The coordination chemistry of indium(III) and thallium(III) in liquid ammonia solution. (Manuscript).
Place of Publication:Uppsala
ISBN for printed version:91-576-7020-x
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:metallic elements, ions, ammonia, phosphorus, solvents, solutions, ligands, complexing, chemicophysical properties
Keywords:coordination, d10 metal ions, copper(II), mercury(II) halides, liquid ammonia, phosphite, phosphine, solution, EXAFS
URN:NBN:urn:nbn:se:slu:epsilon-561
Permanent URL:
http://urn.kb.se/resolve?urn=urn:nbn:se:slu:epsilon-561
ID Code:779
Department:(NL, NJ) > Dept. of Chemistry (until 131231)
Deposited By: Kersti Nilsson
Deposited On:04 Mar 2005 00:00
Metadata Last Modified:02 Dec 2014 10:07

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