74974-60-0Relevant articles and documents
Reactions and structures in the gallium(III)/indium(III)-N,N- dimethylthioformamide systems
Topel, ?nder,Persson, Ingmar,Lundberg, Daniel,Ullstr?m, Ann-Sofi
, p. 220 - 224 (2011)
The structure of the N,N-dimethylthioformamide (DMTF) solvated gallium(III) ion has been determined in solution by means of extended X-ray absorption fine structure (EXAFS) spectroscopy. The gallium(III) ion is four-coordinate in tetrahedral fashion with a mean Ga-S bond distance of 2.233(2) in DMTF solution. At the dissolution of indium(III) perchlorate or trifluoromethanesulfonate in DMTF coordinated solvent molecules are partly reduced to sulfide ions, and a tetrameric complex with the composition [In4S4(SHN(CH 3)2)12]4+ is formed. The structure of the solid tetrameric complex in the perchlorate salt was solved with single crystal X-ray diffraction. Four indium(III) ions and four sulfide ions form a highly symmetric heterocubane structure where each indium binds three bridging sulfide ions and each sulfide ion binds three indium(III) ions with a mean In-S bond distance of 2.584(1) , and S-In-S angles of 90.3(1)°. Each indium(III) additionally binds three DMTF molecules at significantly longer mean In-S bond distance, 2.703(1) ; the S-In-S angles are in the range 80.3-90.4°. Large angle X-ray scattering data on a DMTF solution of indium(III) trifluoromethanesulfonate show that the same tetrameric species characterized in the solid state is also present in solution, whereas the EXAFS measurements only give information about the In-S bond distances due to the short core hole lifetime.
Dimethyl sulfoxide solvates of the aluminium(III), gallium(III) and indium(III) ions. A crystallographic, EXAFS and vibrational spectroscopic study
Molla-Abbassi, Alireza,Skripkin, Mikhail,Kritikos, Mikael,Persson, Ingmar,Mink, Janos,Sandstroem, Magnus
, p. 1746 - 1753 (2007/10/03)
The isostructural hexakis(dimethyl sulfoxide)-aluminium(III), -gallium(III) and -indium(III) iodides crystallise in the trigonal space group R3 (no. 148), Z = 3, at 295 ± 1 K. The metal ions are located in a 3 symmetry site with M-O bond distances of 1.894(4), 1.974(4) and 2.145(3) A, 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) A, V = 2467.2(5) A3 for [Al(OS(CH 3)2)6]I3, a = 10.927(2), c = 23.868(4) A, V = 2468.1(6) A3 for [Ga(OS(CH 3)2)6]I3, and a = 11.358(2), c = 21.512(4) A, V = 2403.5(7) A3 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. The Royal Society of Chemistry 2003.