The anodic oxidation of molybdenum metal in MeOH at both low anodic and cathodic current density (0.025 A/cm(2)) and electrolyte temperatures kept below 20 degreesC provides sn efficient approach to Mo(OMe)(6) (I). W(OMe)(6) (II) can be obtained from the electrolytes, prepared via anodic dissolution of tungsten, by fractional crystallization. The symmetrically independent units in the structures of I and II, being isomorphous, follow the C-1 (slightly distorted D-2d) symmetry. Theoretical calculations performed for a free molecule of I indicate that this low symmetry may be the result of the packing of the molecules in the crystal, structure and also an inherent property imposed by the bonding in this compound. Crystal data for I: Mo(OMe)(6) at 22 degrees C, a = 7.0976(13), b = 6.6103(12), and c = 12.286(2) Angstrom, beta = 90.068(3)degrees, V= 576.41(18) Angstrom (3), monoclinic P2/n, Z = 2. Crystal data for II: W(OMe)(6) at 22 degreesC, a = 7.1164(19), b = 6.6414(18), and c = 12.304(3) Angstrom, beta = 90.047(5)degrees, V = 581.5(3) Angstrom (3), monoclinic P2/n, Z = 2.