Low-valent trimethylphosphine cobalt compounds are oxidized by tellurium, selenium, or sulfur to give the title compounds. Several high-yield syntheses are described. The crystal and molecular structures of (Me3P)3CoX3Co(PMe3)3 (1: X = Te. 2: X = Se. 3: X = S) have been determined by single crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic space group P21/n; a = 933.8(6) pm. b = 1488.3(6) pm. c = 1257.9(6) pm. β = 92.82(6)°. Z = 2.
Complex 2 crystallizes in the triclinic space group P1, a = 1785.6(7) pm. b = 1599.7(7) pm. c = 928.9(5) pm. α = 87.8(1)°. β = 85.2(1)°. γ = 73.3(1)°. Z = 3.
Complex 3 crystallizes in the monoclinic space group P21/c; a = 952.6(5) pm. b = 1868.7(8) pm. c - 1893.1(8) pm. β = 90.19(6)°. Z = 4.
All three structures contain centrosymmetric molecules with planar Co2X2 rings. In solution dissociation of phosphine ligands occurs followed by slow decomposition to produce [(Me3P)2Co(PMe2)]2 among other products. 1 reacts with carbon monoxide to afford a ditelluride [(Me3P)2(CO)2Co]2Te2. but no corresponding derivatives of 2 or 3 were obtained.
© 1946 – 2014: Verlag der Zeitschrift für Naturforschung
This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.