TRANSITION-METAL-SUBSTITUTED ALANES - SYNTHESIS AND SPECTROSCOPIC STUDIES AND THE STRUCTURE OF (ETA(5)-C5H5)(CO)(2)FE-AL[(CH2)(3)NME(2)]((I)BU)

Salt elimination between X-Al[(CH2)(3)NMe(2)](R) and Y-Al(X)(2)(Do) (X, Y = H, Cl, Br; R = Cl, Br, (i)Bu, CH(2)(t)Bu; Do = NMe(3), quinuclidine, THF) and [L(CO)(n)M][K] (M = Fe, Ru, Co; L = CO, PMe(3), eta(5)-C5H5; n = 1-3) in THF solution quantitatively gives the transition-metal-substituted alanes L(CO)(n)M-Al[(CH2)(3)NMe(2)] (R) (2a-h) and L(CO)(n)M-Al(X)(2)(Do) (2k-m). The new compounds were characterized by means of elemental analysis and H-1, C-13, P-31, and Al-27 NMR, EI-MS, and infrared Y(CO) and Y(Al-H) data. 2a-m constitute rare examples of nonbridged direct transition-metal-aluminum bonds. Those bonds are rather polarized in a Fe-delta-Al-delta+ fashion and are thus highly reactive toward cleavage in the course of electrophilic or nucleophilic attack. X-ray single crystal data for 2a, (eta(5)-C5H5)(Co)(2)-Fe-Al[(CH2)(3)NMe(2)]((i)Bu): monoclinic, P2(1)/n, a = 868.0(2) Angstrom, b = 13.468(2) Angstrom, c 15.213(3) Angstrom, beta = 101.79(1)degrees, V= 1741 Angstrom(3), Z = 4, R = 0.0536 (R(w) = 0.0483). The sigma(Fe-Al) bond length is 2 456(1) Angstrom. 2a-d are used as candidates to generate intermetallic Fe/Al and Co/Al thin films by low-pressure MOCVD.