Synthesis and characterization of polynuclear chromium carbonyl tetraanions Academic Article uri icon

abstract

  • Polynuclear chromium carbonyl complexes of the general formula [Cr4(CO)12(μ3-OR)4]4- (R = H, C6H5) have been prepared as their Et4N+ salts. Reaction of Cr(CO)6 with excess hydroxide ion in aqueous THF solution yields [Cr4(CO)12(μ3-OH)4]4-. The X-ray structure of [Et4N]4[Cr4(CO)12(M3-OH)4] has been determined. The structural features of the tetraanion consist of a cubane-like A4B4 (A = chromium, B = oxygen) arrangement with triply bridging μ3-hydroxide groups and Cr(CO)3 units. The Cr-Cr distance within the Cr4O4 core is nonbonding (3.33 (5) Å (average)), consistent with a closed-shell metal configuration. The crystals are monoclinic (space group I2/a) with cell constants a = 21.827 (7) Å, b = 12.236 (2) Å, c = 22.899 (4) Å, β = 116.49 (2)°, V = 5474 (5) Å3, and Z = 8. The, μ3-phenoxide derivative, [Et4N]4[Cr4(CO)12(μ3-OC6H5)4], has been prepared by treatment of Cr(CO)3(CH3CN)3 with [Et4N] [OC6H5] in equimolar concentrations and characterized by spectroscopic methods. © 1985, American Chemical Society. All rights reserved.

author list (cited authors)

  • McNeese, T. J., Mueller, T. E., Wierda, D. A., Darensbourg, D. J., & Delord, T. J.

citation count

  • 16

publication date

  • October 1985