GROUP-13 HALIDES AND HYDRIDES WITH O-(AMINOMETHYL)PHENYL SUBSTITUENTS

Two new group 13 dihalides of the type ArMX(2) (Ar = o-[(dimethylamino)methyl]phenyl; MX(2) = AlBr2 (4), GaCl2 (5)) have been prepared via the salt-elimination reactions of o-(Me(2)NCH(2))C6H4Li with MX(3). The reaction of 4 or 5 with LiAlH4 afforded the corresponding aluminum dihydride dimer [Ar(H)AI(mu-H)](2) (6). Treatment of 5 with LiGaH4 resulted in the monomeric gallium dihydride ArGaH2 (7), which rearranged to the monohydride Ar2GaH (8) upon standing in toluene solution at -20 degrees C. Compounds 4-8 have been characterized by X-ray crystallography, elemental analysis, NMR, and mass spectroscopy. Crystal data for 4: monoclinic, space group P2(1)/c, a = 9.535(3) Angstrom, b = 10.209(4) Angstrom, c = 12.622(5) Angstrom beta = 92.70(2)degrees, V = 1227.3(4) Angstrom(3), Z = 4, R = 0.0491. Crystal data for 5: monoclinic, space group P2(1)/c, a = 9.371(1) Angstrom, b = 13.143(2) Angstrom, c 10.286(1) Angstrom,beta = 116.38(1)degrees, V = 1134.9(2)Angstrom(3), Z = 4, R = 0.0311. Crystal data for 6: monoclinic, space group P2(1)/n, a = 9.007(1) Angstrom, b = 11.131(1) Angstrom, c = 10.279(1) Angstrom,beta = 105.64(1)degrees, V = 992,3(5) Angstrom(3), Z = 4, R = 0.0684. Crystal data for 7: monoclinic, space group P2(1)/c, a = 9.511(3) Angstrom, b = 12.588(3) Angstrom, c = 16.92(1) Angstrom, beta = 102.73(3)degrees, V = 1976(1)Angstrom(3), Z = 8, R = 0.086. Crystal data for 8: orthorhombic, space group P2(1)2(1)2(1), a = 9.615(1) Angstrom, b = 10.050(1) Angstrom, c = 17.856(2) Angstrom, V = 1717.9(9) Angstrom(3), Z = 4, R = 0.052.