Preparations and Structures of cis-[Mo2(S2CNC4H4)2(O2CCH3)2OPPh3] and [Mo2(S2PEt3)(O2CCH3)3OPEt3](BF4): Two Quadruply Bonded Dimers Involving Dithio Acid Ligands
The dithiocarbamate of pyrrole (pdc) reacts with molybdenum acetate and triphenylphosphine oxide to give cis-[Mo2(pdc)2(O2CCH3)2OPPh3], which crystallizes with benzene with 1½ molecules of solvent per dimer in the triclinic space group P1 with unit cell parameters a = 11.777 (2) Å, b = 16.690 (2) Å, c = 11.535 (3) Å, α = 95.4 (2)°, β = 102.07 (2)°, γ = 84.23 (1)°, V = 2197.9 Å3, and Z = 2. The reaction of molybdenum acetate with the zwitterionic S2CPEt3 in the presence of HBF4 yields the dimer [Mo2(S2CPEt3)(O2CCH3)3OPEt3](BF4) which crystallizes in the monoclinic space group P21/c with unit cell parameters a = 13.186 (2) Å, b = 14.403 (3) Å, c = 17.882 (4) Å, β = 106.97 (1)°, V = 3248.3 Å3, and Z = 4. In both dimers, one molybdenum is axially coordinated to the oxygen of the phosphine oxide and the other to the oxygen of an acetate on an adjacent dimer. The Mo-O distances for the oxygen of the phosphine oxide are the shortest observed for axial coordination. Both sulfur ligands are in the dithio acid resonance form.
Baird, D. M., Fanwick, P. E., & Barwick, T. (1985). Preparations and Structures of cis-[Mo2(S2CNC4H4)2(O2CCH3)2OPPh3] and [Mo2(S2PEt3)(O2CCH3)3OPEt3](BF4): Two Quadruply Bonded Dimers Involving Dithio Acid Ligands. Inorganic Chemistry, 24, (23), 3753 - 3758. https://doi.org/10.1021/ic00217a012. Retrieved from https://nsuworks.nova.edu/cnso_chemphys_facarticles/21