Diphenyl sulphox1de complexes of thorium(IV)

Abstract

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.