The reaction of trialkylaluminum derivatives, R(3)Al(R = Me, Et, i-Bu), and trimethylgallium with the distannoxane (Ph(3)Sn)(2)O yields R(2)MOSnPh(3) (M = Al, R = Me (1a); Et (1b), i-Bu (1c); M = Ga, R = Me (2)) and the corresponding organotin compound, RSnPh(3). Attempts to disrupt the Al-O bridge bonds of [R(2)Al(mu-OSnPh(3))](n) (R Me (1a), Et (1b) and form stable adducts with diethyl ether failed, but 4-picoline gives a 1:1 complex. The resulting derivatives have been characterized by H-1 and C-13:NMR spectroscopy. The structure of la was determined by single-crystal X-ray diffraction techniques and was found to be in the triclinic space group P $$($) over bar 1 with cell constants a = 9.076(1) Angstrom, b = 9.733(2) Angstrom, c 13.084(3) Angstrom, alpha = 71.03(2)degrees, beta = 74.22(1)degrees, gamma = 65.05(1)degrees, and Z = 1. The structure was refined to a final R = 2.6% (R(w) = 3.9%) based on 3185 (I > 2.5 sigma(I)) observed reflections. The molecule exists as a dimer, (Me(2)AlOSnPh(3))(2), with Al-O bond distances of 1.84 Angstrom and Sn-O bond distances of 1.98 Angstrom. Both aluminum and tin centers in the dimer are in a pseudotetrahedral environment.