Title full: Chemical and x-ray structural characterization of diphenylcarbazone and diphenylthiocarbazone complexes of molybdenum(VI), (n-Bu4N)[MoO2(C6H5NNC(X)NNC 6H5)(C6H5NNC(X)NN(H)C 6H5)] (X = O or S) and (n-Bu4N)[MoOCl3(C6H5NNC(O)NN C6H5)]; isolation of 2,3-diphenyltetrazolium-5-thiolate, C6H5NNC(S)NNC6H5, from the reaction of diphenylthiocarbazone with molybdate. Reaction of α-(Bu4N)4[Mo8O26] with diphenylcarbazone (dpcH2) yields the red crystalline complex (Bu4N)[MoO2(C6H5NNC(O)NNC 6H5)(C6H5(H)NNC(O)NNC 6H5)] (I), a complex displaying two distinct chelate ring types. Treatment of I with HCl yields (Bu4N)[MoOCl3(C6H5NNC(O)NNC 6H5)] (III), a pseudo-octahedral complex with the [MoOCl3]+ core. The reaction of α-(Bu4N)4[Mo8O26] with diphenylcarbazone (dptcH2) gave a complex analogous to I, (Bu4N)[MoO2(C6H5NNC(S)NNC 6H5)(C6H5(H)NNC(S) NNC6H5)] (II) and, surprisingly, 2,3-diphenyltetrazolium-5-thiolate, C6H5NNC(S)NNC6H5 (IV). Complex I displays a pseudo-octahedral geometry with MoO4N2 coordination and presents distinct geometries for the chemically inequivalent ligand types (dpc)2- and (dpcH)-. The structure of II is analogous to that of I with MoO2N2S2 coordination geometry but, more significantly, reveals the site of protonation of the (dptcH)- ligand as the terminal exocyclic nitrogen. Crystal data: I, monoclinic space group P21/n, a = 11.026(3), b = 21.600(5), c = 18.851(4) Å, β = 98.04(1)°, V = 4445.1(12) Å3, 2804 reflections, R = 0.065; II, monoclinic space group P21/c, a = 12.209(3), b = 20.090(4), c = 19.097(2) Å, β = 96.45(1)°, V = 4654.4(9) Å3, 3835 reflections, R = 0.047; III, P21/n, a = 14.853(2), b = 15.698(4), c = 17.062(4) Å, β = 90.10(1)°, V = 3978.2(10) Å3, 3128 reflections, R = 0.082; IV, C2/c, a = 14.755(2), b = 12.193(2), c = 6.958(2) Å, β = 97.42(2)°, V = 1241.3(8), 1055 reflections, R = 0.047.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry