86884-85-7Relevant articles and documents
Decomposition of monochlorogallane, [H2GaCl]n, and adducts with amine and phosphine bases: Formation of cationic gallane derivatives
Tang, Christina Y.,Downs, Anthony J.,Greene, Tim M.,Marchant, Sarah,Parsons, Simon
, p. 7143 - 7150 (2008/10/09)
Thermal decomposition of monochlorogallane, [H2GaCl] n, at ambient temperatures results in the formation of subvalent gallium species. To Ga[HGaCl3], previously reported, has now been added a second mixed-valence solid, Ga4-[HGaCl3] 2[Ga2Cl6] (1), the crystal structure of which at 150 K shows a number of unusual features. Adducts of monochlorogallane, most readily prepared from the hydrochloride of the base and LiGaH4 in appropriate proportions, include not only the 1:1 molecular complex Me 3P·GaH2Cl (2), but also 2:1 amine complexes which prove to be cationic gallane derivatives, [H2Ga(NH2R) 2]+Cl-, where R = tBu (3a) or sBu (3b). All three of these complexes have been characterized crystallographically at 150 K.
Dichlorogallane (HGACl2)2: Its molecular structure and synthetic potential
Nogai, Stefan,Schmidbaur, Hubert
, p. 4770 - 4774 (2008/10/08)
Dichlorogallane (HGaCl2)2 is readily prepared from gallium trichloride and triethylsilane in quantitative yield. Its crystal structure has been determined by single crystal X-ray diffraction. In the chlorine-bridged dimers of crystallographically imposed C2h symmetry, the terminal hydrogen atoms are in trans positions. In the reaction with 2 equiv of triethylphosphine, the mononuclear complex (Et3P)GaHCl2 is formed. Thermal decomposition of (HGaCl2)2 affords hydrogen gas and quantitative yields of GaCl2 as mixed-valent Ga[GaCl4]. Treatment of this product with triethylphosphine gives the symmetrical, Ga-Ga-bonded gallium(II) complex [GaCl2(PEt3)]2 with an ethane-type structure and with the phosphine ligands in a single-trans conformation. The corresponding [GaBr2(PEt3)]2 complex is prepared from Ga[GaBr4] and has an analogous structure. (Et3P)GaCl3 has been synthesized and structurally characterized as a reference compound.
A simple high-yield synthesis of gallium(I) tetrachlorogallate(III) and the reaction of digallium tetrachloride tetrahydrofuran solvate with 1,2-diols
Schmidt, Eva S.,Schier, Annette,Mitzel, Norbert W.,Schmidbaur, Hubert
, p. 337 - 341 (2007/10/03)
Gallium(I) tetrachlorogallate(III) Ga[GaCl4] was prepared in quantitative yield by thermal decomposition of dichlorogallane [HGaCl2]2, which is readily available from Et3SiH and [GaCl3]2. The reaction of catechol with solutions of this gallium(I) tetrachlorogallate(III) in tetrahydrofuran leads to the evolution of hydrogen gas and affords a dinuclear gallium(III) complex with penta-coordinate metal atoms chelated and bridged by mono-deprotonated catechol ligands. In the crystalline phase tetrahydrofuran molecules are hydrogen-bonded to the hydroxy groups: [Ga(1,2-OC6H4OH)Cl2(C4H 8O)]2. The reaction with pinacol also gives hydrogen and the analogous product [Ga(OCMe2CMe2OH)Cl2(C4H 8O)]2. The structures of the two compounds have been determined by X-ray diffraction. A mechanism of the new reaction has been proposed which involves oxidative addition of the diol to the solvate (THF)Cl2Ga-GaCl2(THF) present in the tetrahydrofuran solution to give a gallium hydride intermediate.