Research output: Contribution to journal › Article › peer-review
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, János; Sandström, Magnus.
In: Dalton Transactions, No. 9, 07.05.2003, p. 1746-1753.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Dimethyl sulfoxide solvates of the aluminium(III), gallium(III) and indium(III) ions. A crystallographic, EXAFS and vibrational spectroscopic study
AU - Molla-Abbassi, Alireza
AU - Skripkin, Mikhail
AU - Kritikos, Mikael
AU - Persson, Ingmar
AU - Mink, János
AU - Sandström, Magnus
PY - 2003/5/7
Y1 - 2003/5/7
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=10844224549&partnerID=8YFLogxK
U2 - 10.1039/b212140a
DO - 10.1039/b212140a
M3 - Article
AN - SCOPUS:10844224549
SP - 1746
EP - 1753
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 9
ER -
ID: 40044510