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

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Tartalom: http://pubs.rsc.org/en/Content/ArticleLanding/2003/DT/b21...
Archívum: MTA Könyvtár
Gyűjtemény: Status = Published



Type = Article
Cím:
Dimethyl sulfoxide solvates of the aluminium(III), gallium(III) and indium(III) ions. A crystallographic, EXAFS and vibrational spectroscopic study
Létrehozó:
Molla-Abbassi, A.
Skripkin, M.
Kritikos, M.
Mink, János
Dátum:
2003
Téma:
QD Chemistry / kémia
QD03 Inorganic chemistry / szervetlen kémia
TK Electrical engineering. Electronics Nuclear engineering / elektrotechnika, elektronika, atomtechnika
Tartalmi leírás:
The isostructural hexakis( dimethyl sulfoxide)-aluminium(III),
-gallium(III) and -indium(III) iodides crystallise in the trigonal
space group R(3) over bar ( no. 148), Z = 3, at 295 +/- 1 K. The metal
ions are located in a (3) over bar symmetry site with M-O bond
distances of 1.894(4), 1.974(4) and 2.145(3) Angstrom, and M-O-S bond
angles of 127.1(3), 124.1(3) and 123.1(2)degrees, for M = Al, Ga and
In, respectively. The unit cell parameters are a = 10.762(2), c =
24.599(3) Angstrom, V = 2467.2(5) Angstrom(3) for
[Al(OS(CH3)(2))(6)]I-3, a = 10.927(2), c = 23.868(4) Angstrom, V =
2468.1(6) Angstrom(3) for [Ga(OS(CH3)(2))(6)]I-3, and a = 11.358(2), c
= 21.512(4) Angstrom, V = 2403.5(7) Angstrom(3) for
[In(OS(CH3)(2))(6)]I-3. 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)]I-3, 491 and 495 cm(-1) for
[Ga(OS(CH3)(2))(6)]I-3, and 444 and 440 cm(-1) for
[In(OS(CH3)(2))(6)]I-3, respectively.
Típus:
Article
PeerReviewed
Formátum:
text
Azonosító:
Molla-Abbassi, A. and Skripkin, M. and Kritikos, M. and Mink, János (2003) Dimethyl sulfoxide solvates of the aluminium(III), gallium(III) and indium(III) ions. A crystallographic, EXAFS and vibrational spectroscopic study. DALTON TRANSACTIONS (9). pp. 1746-1753. ISSN 1477-9226
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