24597-12-4Relevant articles and documents
Dichlorogallane (HGACl2)2: Its molecular structure and synthetic potential
Nogai, Stefan,Schmidbaur, Hubert
, p. 4770 - 4774 (2002)
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.
Gallium and gallium dichloride, new solid-state reductants in preparative transition metal chemistry. New, lower temperature syntheses and convenient isolation of hexatantalum tetradecachloride octahydrate
Hay, Daniel N. T.,Swenson, Dale C.,Messerle, Louis
, p. 4700 - 4707 (2002)
Reduction of TaCl5 with either Ga or Ga2Cl4, in the presence of NaCl, in a sealed borosilicate glass ampule at 500°C, followed by aqueous Soxhlet extraction and treatment with SnCl2 and hydrochloric acid, yielded Ta6(μ-Cl)12-Cl2 (OH2)4·4H2O in 92% (Ga) or 96% (Ga2Cl4) yield. Ga2Cl4, a probable intermediate in the Ga-based reduction, is a more convenient reductant than Ga because it is readily dispersed in the reaction mixture, and these mixtures do not require homogenizations in order to afford high yields. Ta6(μ-Cl)12Cl2 (OH2)4·4H2O was converted by ligand exchange to the first tetraalkylammonium derivative, [N(CH2Ph)Bu3]4[Ta6 [μ-Cl)12Cl6], of the reduced cluster core Ta6(μ-Cl)122+, in 88% yield. [N(CH2Ph)Bu3]4[Ta6 (μ-C)12Cl6] crystallizes from 1,2-dichloroethane/toluene mixtures in two crystalline morphologies, a nonsolvated cubic form and a solvated needle form. The solid-state molecular structures of both crystalline morphologies of [N(CH2Ph)Bu3]4[Ta6 (μ-Cl)12Cl6] consist of octahedral, 16 VEC hexatantalum cluster anions with an average Ta-Ta distance of 2.900[2] A, a Ta-Cl(bridge) distance of 2.463[2] A, a Ta-Cl(terminal) distance of 2.567[5] A, and a Ta-Cl-Ta angle of 72.1[1]° for the cubic form, and for the solvated needle morphology, an average Ta-Ta distance of 2.900[1] A, a Ta-Cl(bridge) distance of 2.461[1]A, a Ta-Cl(terminal) distance of 2.567[3] A, and a Ta-Cl-Ta angle of 72.19[7]°.
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.
