We report the synthesis and characterization of the first eta(3)-1,3,5-trimethyl-1,3,5-triazacyclohexane (Me(3)TAC) alkoxo complexes. Dehydration of [Co(H2O)(6)](X)(2) with 2,2-dimethoxypropane or HC(OMe)(3) and subsequent treatment with Me(3)TAC results in the formation of the methoxo cube fragment clusters [{(Me(3)TAC)Co}(3)(OMe)(4)]- (X)(2) (X = B(C6F5)(4) (2a) and B(m-C6H3(CF3)(2))(4) (2b)). 2a crystallizes in the triclinic space group P (1) over bar (a = 13.857-(2) Angstrom, b = 16.843(3) Angstrom, c = 19.318(2) Angstrom, alpha = 79.23(2)degrees, beta = 76.855(13)degrees, gamma = 70.10(2)degrees, Z = 2) and 2b in the monoclinic space group P2(1) (a = 12.710(3) Angstrom, b = 23.251(3) Angstrom, c = 18.702(4) Angstrom, B = 101.16(2)degrees, Z = 2). The cations contain a {Co-3(OMe)(4)} cube fragment core with an eta(3)-Me(3)TAC bonded to each cobalt atom. Me(3)TAC is bonded unsymmetrically due to hydrogen-bonding interactions with the anions. This broken symmetry can also be observed as solvent-, anion-, and H/D isotope-dependent splitting of the signals in H-1 and H-2 NMR. A byproduct of the reaction is the protonated Me(3)TAC. The analogous monoacid adduct Me(3)TAC . HCl has been characterized by X-ray crystallography (orthorhombic space group Pbca, a = 11.0366(9) Angstrom, b 12.2986(6) Angstrom, 13.9949(7) Angstrom, Z = 8).