TRANSITION-METAL-SUBSTITUTED GALLANES - SYNTHESIS AND SPECTROSCOPIC STUDIES OF HIGHLY POLAR SIGMA(M-GA) BONDS, STRUCTURES OF TRANS-(PH(3)P)(CO)(3)CO-GA[(CH2)(3)N(C2H5)(2)]R (R=CL, CH3) AND (ETA(5)-C5H5)(CO)(2)FE-GACL2[N(CH3)(3)]

The salt elimination reaction of the transition carbonyl metallates [L(CO)(n)M](Na/K) (M = Cr, Mo, W, Mn, Re, Fe, Co, Ni; L = CO, eta(5)-C(5)R(5), PR(3); n = 1-4; R = alkyl, aryl) with the base-stabilized galliumhalides Cl(a)GaR(3-a)(Do) (R = H, alkyl, halide; Do = THF, N(CH3)(3), NC7H13) or ClaGa[(CH2)3NR'(2)](R)(2-a) yielded almost quantitatively the transition metal-substituted, gallanes [L(CO)(n)M](a)GaR(3-a)(Do) and [L(CO)(n)M]Ga-a[(CH2)(3)NR'(2)](R)(2-a), respectively. Residual halide functionalities in these complexes were selectively replaced by various other groups. The new compounds were characterized by means of elemental analysis, H-1-, C-13-, P-31-NMR, MS, and IR nu(CO) data. The single-crystal X-ray structure analysis of trans-(Ph(3)P) (CO)(3)Co-Ga[(CH2)(3)N(C2H5)(2)] (R) (6S: R = Cl, 6t: R = CH3) showed sigma(Co-Ga) lengths of 237.78(4) and 249.5(1) pm, respectively. A short sigma(Fe-Ga) contact of 236.18(3) pm was found for (eta(5)-C5H5)(CO)(2)Fe-GaCl2[N(CH3)(3)] (5a). Low-pressure MOCVD experiments were performed to give thin films of analytically pure CoGa alloy.