Formation and Characterization of the Cationic Gallane Derivatives [(RH2N)(2)GaH2]Cl (R = Me or iPr) and [{(iPrH(2)N)GaH(2)NHiPr}(2)GaH2]Cl

The reaction of LiGaH4 with an excess of the hydrochloride of a primary amine RNH2 in ether solution yields in [(RH2N)(2)GaH2]Cl (R = Me, 1, or iPr, 2) additional examples of cationic gallane derivatives. The cation [(iPrH(2)N)(2)GaH2](+) reacts further with LiGaH4, also in ether solution, with H-2 elimination and f ormation of the trigallium cationic derivative [{(iPrH(2)N)GaH(2)NHiPr)(2)GaH2]Cl, 3. Prolonged standing of [(iPrH(2)N)(2)GaH2]Cl in the presence of LiCl results in partial exchange of Ga-H by Ga-Cl bonds, with the isolation in low yield of crystals, 4, of [(iPrH(2)N)(2)GaH2]Cl in which about 7% of the H atoms attached to Ga were replaced by Cl. All of the compounds 1-4 having been characterized crystallographically, the results are discussed in relation to the different reaction pathways open to [RNH3]Cl and LiMH4 (M = At or Ga). ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).