REACTIVITY OF THE MO(SX) FUNCTIONAL-GROUPS IN THIOMOLYBDATE AND OXOTHIOMOLYBDATE COMPLEXES TOWARD CARBON-DISULFIDE - SYNTHESIS AND REACTIVITY OF TRITHIOCARBONATE AND PERTHIOCARBONATE COMPLEXES OF MO(IV) AND MO(V) AND STRUCTURAL CHARACTERIZATION OF TRANS-[PH4P]2[MO(S)(CS4)2].DMF (I), CIS-[PH4P][ET4N][MO(S)(CS4)2] (II), CIS-SYN-[PH4P]2[MO2(S)2(MU-S)2(CS4)2].1/2DMF (III), SYN-[PH4P]2[MO2(S)2(MU-S)2(CS3)2] (IV), AND SYN-[ET4N]2[MO2(O)2(MU-S)2(CS4)(CS3)] (V)

The syntheses and structures of the diamagnetic complexes trans-[Ph4P]2[Mo(S)(CS4)2].DMF (I), cis-[Ph4P][Et4N][Mo(S)(CS4)2] (II), cis-syn-[Ph4P]2[Mo2(S)2(mu-S)2(CS4)2].1/2DMF (III), syn-[Ph4P]2[Mo2(S)2(mu-S)2(CS3)2] (IV), and syn-[Et4N]2[Mo2(O)2(mu-S)2(CS4)(CS3)] (V) and the syntheses of syn-[Et4N]2[Mo2(O)2(mu-S)2(eta(2)-S4)(eta(2)-CS3)] (VI), syn-[Et4N]2[Mo2(O)2(mu-S)2(eta(2)-S2)(eta(2)-CS3)] (VII), and syn-[Et4N]2[Mo2(O)2(mu-S)2(eta(2)-CS3)2] (VIII) are reported. Compounds I, II and V crystallize in the space groups P2(1)/a, Pbcm, and Pnca, respectively. Compounds III and IV both crystallize in the space group P1BAR. The cell dimensions are as follows. I: a = 19.769 (7) angstrom, b = 13.345 (5) angstrom, c = 21.647 (8) angstrom, beta = 111.21 (3)-degrees, Z = 4. II: a = 8.024 (2) angstrom, b = 18.371 (5) angstrom, c = 27.183 (5) angstrom, alpha = beta = gamma = 90-degrees, Z = 4. III: a = 10.748 (3) angstrom, b = 12.262 (4) angstrom, c = 22.377 (7) angstrom, alpha = 75.66 (3)-degrees, beta = 87.70 (2)-degrees, gamma = 80.49 (3)-degrees, Z = 2. IV: a = 10.655 (3) angstrom, b = 13.720 (5) angstrom, c = 19.764 (5) angstrom, alpha = 90.90.(3)-degrees, beta = 102.43 (2)-degrees, gamma = 112.08 (2)-degrees, Z = 2. V: a = 13.005 (4) angstrom, b = 31.879 (8) angstrom, c = 15.540 (4) angstrom, alpha = beta = gamma = 90-degrees, Z = 8. Crystallographic data for the four structures were obtained on an automatic diffractometer employing Mo K-alpha radiation. The refinement of the structures by full-matrix least-squares methods was based on 2622 unique reflections (2-theta(max) = 40-degrees, I > 3-sigma(I)) for I, on 1424 unique reflections (2-theta(max) = 40-degrees, I > 3-sigma(I)) for II, on 2648 unique reflections (2-theta(max) = 40-degrees, I > 3-sigma(I)) for III, on 3998 unique reflections (2-theta(max) = 45-degrees, I > 3-sigma(I)) for IV, and on 2160 unique reflections (2-theta(max) = 45-degrees, I > 3-sigma(I)) for V. Anisotropic temperature factors were used for all non-hydrogen atoms in I-V. At the current stage of refinement on 339 parameters for I, 148 parameters for II, 371 parameters for III, 578 parameters for IV, and 256 parameters for V with all atoms present in the asymmetric units, R(w) = 0.055, 0.081, 0.075, 0.030, and 0.078, respectively. The structures of the isomeric complex anions in I and II show the Mo(IV) ions in square pyramidal coordination with two CS4(2-) ligands in the equatorial plane (trans to each other for I and cis for II) and a terminal sulfido axial ligand lying approximately 0.7 angstrom above the equatorial plane. The [Mo2(mu(2)-S)2(S)2(L)2]2- dimeric units in III and IV contain the [Mo2(mu(2)-S)2(S)2]2+ cores with five-coordinate Mo(V) ions, the Mo = S units in the syn configuration, and L = CS4(2-) terminal ligands in III and L = CS3(2-) terminal ligands in IV. The structure of V shows a dimeric asymmetric anion that is a "mixed-ligand" analogue of III and IV with one CS3(2-) and one CS4(2-) as terminal ligands and Mo = O units in place of the Mo = S units. Selected structural features for I and II include the following: Mo = S, 2.126 (3) and 2.127 (4) angstrom; Mo-S(L), 2.383 (3) and 2.376 (3) angstrom; Mo-S-S(L), 2.326 (3) and 2.320 (3) angstrom. Selected structural features for III: Mo-Mo, 2.840 (3) angstrom; Mo-S(b), 2.316 (5) angstrom; Mo = S, 2.108 (5) angstrom; Mo-S(b)-Mo, 75.6-degrees; S(b)-Mo-S(b), 101.4-degrees. The Mo-Mo distance in IV is found at 2.823 (1) angstrom and in V at 2.835 (2) angstrom. Other selected structural features of IV and V: Mo-S(b), 2.300 (7) and 2.305 (5) angstrom; Mo-S(b)-Mo, 75.6 and 75.4-degrees; S(b)-Mo-S(b), 100.8 and 100.5-degrees. The Mo = S bond length in IV is 2.100 (2) angstrom, and the Mo = O bond length in V is 1.68 (1) angstrom. A study of the C-13 NMR spectra of the perthio- and trithiocarbonate complexes shows that the complicated solution behavior of these complexes is dominated by sulfur addition and CS2 elimination reactions.