OXIDATION AND HYDROLYSIS OF TRIS-TERT-BUTYLGALLIUM

The oxidation of GaBu3t with oxygen leads to the formation of [Bu2tGa(mu-OOBu(t))]2 (1). The thermolysis of 1 yields the alkoxide complex [Bu2tGa(mu-OBu(t))]2 (2), which may also be prepared directly from GaBu3t and Bu(t)OH. The reaction of [Bu(t)GaCl(mu-Cl)]2 (3) with oxygen does not result in its oxidation, but may be used in its purification due to the oxidation of the GaBu3t impurities. The hydrolysis of GaBu3t in thf solution, in which it exists as the solvated complex 4, results in the formation of the monomeric hydroxide complex Bu2tGa(OH)(thf) (5). In contrast, the use of non-coordinating solvents results in the trimeric hydroxide [Bu2tGa(mu-OH)]3 (6). Compound 6 is also isolated from the reaction of Bu2tGaCl(thf) (7) with KOH in refluxing thf. The solid state pyrolysis of 6 gives the polymeric oxide [Bu(t)Ga(O)]x (8). All the compounds have been characterized by NMR, IR and mass spectroscopy, while the structures of 1, 2 and 3 have been confirmed by X-ray crystallography. Compound 1 crystallizes in the monoclinic space group C2/m with a = 16.375(2), b = 11.323(2), c = 8.895(2) angstrom and beta = 116.710(12)-degrees, Z = 2, R = 0.042 and R(w) = 0.038. Compound 2 crystallizes in the orthorhombic space group Pbca with a = 15.0072(17), b = 9.8399(8), c = 18.3840(15) angstrom, Z = 4, R = 0.037 and R(w) = 0.041. Compound 3 crystallizes in the monoclinic space group P2(1)/c with a = 6.816(4), b = 6.743(5), c = 17.062(10) angstrom and beta = 95.87(4)-degrees, Z = 2, R = 0.042, R(w) = 0.049.