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.
Some chemical properties of monochlorogallane: Decomposition to gallium(I) trichlorogallate(III), Ga+[GaCl3H]-, and other reactions
Johnsen,Downs,Goode,Greene,Himmel,Mueller,Parsons,Pulham
, p. 4755 - 4761 (2008/10/08)
Thermal decomposition of monochlorogallane, [H2GaCl]n, at ambient temperatures releases H2 and results in the formation of gallium(I) species, including the new compound Ga[GaHCl3], which has been characterized crystallographically at 100 K (monoclinic P21/n, a = 5.730(1), b = 6.787(1), c = 14.508(1) A, β = 97.902(5)°) and by its Raman spectrum. The gallane suffers symmetrical cleavage of the Ga(μ-Cl)2Ga bridge in its reaction with NMe3 but unsymmetrical cleavage, giving [H2Ga(NH3)2]+Cl-, in its reaction with NH3. Ethene inserts into the Ga-H bonds to form first [Et(H)GaCl]2 and then [Et2GaCl]2.
