Dimethyl sulfoxide solvates of the aluminium(III), gallium(III) and indium(III) ions. A crystallographic, EXAFS and vibrational spectroscopic study

Alireza Molla-Abbassi, Mikhail Skripkin, Mikael Kritikos, Ingmar Persson, János Mink, Magnus Sandström

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26 Citations (Scopus)

Abstract

The isostructural hexakis(dimethyl sulfoxide)-aluminium(III), -gallium(III) and -indium(III) iodides crystallise in the trigonal space group R3̄ (no. 148), Z = 3, at 295 ± 1 K. The metal ions are located in a 3̄ symmetry site with M-O bond distances of 1.894(4), 1.974(4) and 2.145(3) Å, and M-O-S bond angles of 127.1(3), 124.1(3) and 123.1(2)°, for M = Al, Ga and In, respectively. The unit cell parameters are a = 10.762(2), c = 24.599(3) Å, V = 2467.2(5) Å3 for [Al(OS(CH 3)2)6]I3, a = 10.927(2), c = 23.868(4) Å, V = 2468.1(6) Å3 for [Ga(OS(CH 3)2)6]I3, and a = 11.358(2), c = 21.512(4) Å, V = 2403.5(7) Å3 for [In(OS(CH 3)2)6]I3. The increasing compression of the octahedral MO6 coordination entities along one three-fold axis for M = Al, Ga and In, respectively, explains why the largest ion indium(III) has the smallest unit cell volume. EXAFS measurements on the dimethyl sulfoxide solvated gallium(III) and indium(III) ions in solution and in the solid perchlorate and trifluoromethanesulfonate salts, show similar bond distances as in the solid iodide solvates. Raman and infrared spectra have been recorded for the hexakis(dimethyl sulfoxide)metal(III) iodides and the nature of the metal-sulfoxide bond has been evaluated by normal coordinate methods. The symmetric and asymmetric M-O stretching modes correspond to the vibrational frequencies 465 and 540 cm-1 for [Al(OS(CH3) 2)6]I3, 491 and 495 cm-1 for [Ga(OS(CH3)2)6]I3, and 444 and 440 cm-1 for [In(OS(CH3)2)6]I 3, respectively.

Original languageEnglish
Pages (from-to)1746-1753
Number of pages8
JournalDalton Transactions
Issue number9
DOIs
Publication statusPublished - 7 May 2003

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Scopus subject areas

  • Inorganic Chemistry

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