The propensity of alkoxide and aryloxide derivatives of tungsten carbonyls to aggregate in solution. Synthesis and X-ray structures of dinuclear, trinuclear and tetranuclear complexes derived from the MeOW(CO)5− anion
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The complex [Et4N] [W(CO)5OMe] (1) has been prepared from the reaction of the photochemically generated W(CO)5THF adduct and [Et4N] [OH] in methanol. Complex 1 was shown to undergo rapid CO dissociation in THF to quantitatively provide the dimeric dianion, [W(CO)4OMe]22-. The resulting THF insoluble salt [Et4N]2 [W(CO)4OMe]2 (2) has been structurally characterized by X-ray crystallography, with the doubly bridging methoxide ligands being in an anti configuration. Complex 2 was found to subsequently react with excess methoxide ligand in a THF slurry to afford the face-sharing octahedron complex [Et4N]3[W2(CO)6(OMe)3] (3) which contains three doubly bridging methoxide groups. In the absence of excess methoxide ligand complex 2 cleanly yields the tetrameric complex [Et4N]4[W(CO)3OMe]4 (4) which has been structurally characterized as a cubane-like arrangement with triply bridging μ3-methoxide groups and W(CO)3 units. Although complex 3 was not characterized in the solid state, the closely related glycolate derivative [Et4N]3[W2(CO)6(OCH 2CH2OH)3] (5) was synthesized and its structure determined by X-ray crystallography. The trianions of complex 5 are linked in the crystal lattice by strong intermolecular hydrogen bonds. Crystal data for 2: space group P21/n, a = 7.696(2), b = 22.019(4), c = 9.714(2) Å, β = 92.22(3)°, Z = 4, R = 6.43%. Crystal data for 4: space group Fddd, a = 12.433(9), b = 24.01 (2), c = 39.29(3) Å, Z = 8, R = 8.13%. Crystal data for 5: space group P212121, a = 11.43(2), b = 12.91(1), c = 29.85(6) Å, Z = 8, R = 8.29%. Finally, the rate of CO ligand dissociation in the closely related aryloxide derivatives [Et4N][W(CO)5OR] (R = C6H5 and 3,5-F2C6H3) were measured to be 2.15 × 10-2 and 1.31 × 10-3 s-1, respectively, in THF solution at 5°C. Hence, the value of the rate constant of 2.15 × 10-2 s-1 establishes a lower limit for the first-order rate constant for CO loss in the W(CO)5OMe- anion, since the methoxide ligand is a better π-donating group than phenoxide. © 1998 Elsevier Science S.A.
author list (cited authors)
Darensbourg, D. J., Klausmeyer, K. K., Draper, J. D., Chojnacki, J. A., & Reibenspies, J. H.