Structure of the Dimethyl Sulfoxide Solvated Thallium(III) Ion in Solution and in the Solid State

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• 作者：Guibin Ma ; Alireza Molla-Abbassi ; Mikael Kritikos ; Andrey Ilyukhin ; Farideh Jalilehvand ; Vadim Kessler ; Mikhail Skripkin ; Magnus Sandströ ; m ; Julius Glaser ; Jan N&auml ; slund ; and Ingmar Persson
• 刊名：Inorganic Chemistry
• 出版年：2001
• 出版时间：December 3, 2001
• 年：2001
• 卷：40
• 期：25
• 页码：6432 - 6438
• 全文大小：83K
• 年卷期：v.40,no.25(December 3, 2001)
• ISSN：1520-510X

文摘

The structure and vibrational spectra of the dimethyl sulfoxide solvated thallium(III) ion have been studied in adimethyl sulfoxide solution and in the solid state. X-ray crystallography shows a trigonal unit cell, space groupRges/entities/thremacr.gif"> (No. 148), for the [Tl(dmso)₆](ClO₄)₃ compound with Z = 3, a = b = 11.9764(13) [11.8995(9)] Å, c =20.802(2) [20.467(2)] Å, and V = 2584.0(5) [2509.9(4)] ų at 295 [150] K. The crystal structure comprises ahighly symmetric hexakis(dimethyl sulfoxide)thallium(III) ion, with thallium in a ges/entities/thremacr.gif"> symmetry site and a Tl-Obond distance of 2.224(3) Å at 295 K. The octahedral TlO₆ kernel is compressed along the threefold axis with anO-Tl-O bond angle of 96.20(11)ges/entities/deg.gif">. The Tl-O-S bond angle of 120.7(2)ges/entities/deg.gif"> corresponds to a Tl···S distance of3.292(2) Å. One perchlorate ion centered on the ges/entities/thremacr.gif"> axis was described by a statistically disordered model. Alow-temperature EXAFS study (10 K) resulted in the Tl-O and Tl···S distances of 2.221(4) and 3.282(6) Å,respectively, consistent with a Tl-O-S bond angle of 120(1)ges/entities/deg.gif">. The low Debye-Waller factors confirm a regularcoordination without the disorder of the dimethyl sulfoxide ligands, which would have resulted from the alternativechoice of space group R3 for the crystal structure. Raman and infrared spectra have been recorded and assigned,with the bands at 435 and 447 cm^-1 corresponding to the vibrational frequency of the symmetric and asymmetricTl-O stretching modes, respectively. EXAFS data of a 0.5 mol dm^-3 thallium(III) trifluoromethanesulfonate ina dimethyl sulfoxide solution were consistent with that of a hexasolvated ion with mean Tl-O and Tl···S distancesof 2.22(1) and 3.33(2) Å, respectively, which correspond to a mean Tl-O-S bond angle of 124(2)ges/entities/deg.gif">. Theanomalously large disorder parameter for the Tl-O distances is consistent with a weak pseudo-Jahn-Teller effect.The ²⁰⁵Tl, ¹³C, and ¹H NMR spectra of the complex in solution show single signals at 1886, 39.5, and 2.3 ppm,respectively.