19854-31-0Relevant articles and documents
Chemistry of methylgallium(III) compounds in protic solvents
Beachley Jr.,Kirss,Bianchini,Royster
, p. 724 - 727 (1987)
The chemical properties of as well as routes to the formation of methylgallium(III) compounds in aqueous acidic solutions and in other protic solvents have been investigated. Aqueous perchloric acid solutions of Me2GaClO4 at room temperature are surprisingly resistant to hydrolytic cleavage of the gallium-carbon bond. Only 14% of the available methyl groups of Me2GaClO4 when dissolved in 0.0171 M HClO4 are converted to CH4 after a 3-month time period. In contrast, Me2GaClO4 undergoes a significantly faster methyl-transfer reaction with Ga(ClO4)3 in aqueous HClO4 solution to form MeGa2+(aq) which in turn hydrolyzes to form Ga3+(aq) and methane. Approximately 36% of the initially available methyl groups form CH4 in 3 months. The dimethylgallium cation also methylates Hg2+(aq) to form MeGa2+(aq) and MeHg+(aq) in aqueous solution, but Me2Ga+(aq) does not react with Al3+(aq), Zn2+(aq), or Na+(aq). In a second series of experiments the methylation of gallium(III) by Me2Co(BDM1,3pn) (BDM1,3pn = {N,N′-propane-1,3-diyl[bis(biacetyl monooxime imino)]}) was investigated in ethanol and acetone solutions by using UV titration and 1H NMR data. The observed stoichiometry of the reaction requires 1 mol of Ga(ClO4)3 for every 2 mol of Me2Co(BDM1,3pn). The identified products are Me2Ga+ and MeCo-(BDM1,3pn)+. In contrast, gallium(III) is not methylated by methylcobalamin in aqueous solution.
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 (2003)
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.