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Diphenyl sulphox1de complexes of thorium(IV)

Savant, VV and Patel, CC (1971) Diphenyl sulphox1de complexes of thorium(IV). In: Journal of The Less-Common Metals, 24 (4). pp. 459-465.

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Official URL: http://dx.doi.org/10.1016/0022-5088(71)90031-2


Thorium(IV) is known to form high coordination-number complexes. An attempt has therefore been made to determine the effect of anions on the coordination complexes of diphenyl sulphoxide (DPSO) with thorium(IV). The complexes formed have the formulae [Th(DPSO)6](ClO4)4, [Th(DPSO)4Cl4], [Th(DPSO)4Br4], [Th(DPSO)6I2]I2, [Th(DPSO)4(NCS)4]and [Th(DPSO)3(NO3)4]. In all the complexes, DPSO is coordinated to the metal ion through its oxygen. The electrical conductances in nitrobenzene and in nitromethane, and ebullioscopic molecular weights in acetonitrile, show that the perchlorate and iodide complexes behave as 1:4 and 1:2 electrolytes, respectively; while the other complexes are monomeric and non-electrolytes. The infrared spectra of the solid complexes indicate the ionic nature of the perchlorate, the bidentate nature of the nitrate and the coordination of the thiocyanate through its nitrogen. [Th(DPSO)4Cl4], [Th(DPSO)4Br4]and [Th-(DPSO)3 (NO3)4]decompose endothermically while [Th(DPSO)6](ClO4)4 and [Th(DPSO)4(NCS)4]decompose exothermically, both in air and in nitrogen. The perchlorate complex has octahedral symmetry around the thorium, the halo- and the thiocyanato complexes are 8-coordinate, probably with square antiprismatic structures, while the nitrate complex is 11-coordinate

Item Type: Journal Article
Publication: Journal of The Less-Common Metals
Publisher: Elsevier Science
Additional Information: Copyright of this article belongs to Elsevier Science.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 16 Jun 2010 07:47
Last Modified: 19 Sep 2010 06:09
URI: http://eprints.iisc.ac.in/id/eprint/28412

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