76429-50-0Relevant academic research and scientific papers
Oxotungsten(IV)-acetylene complexes: Synthesis via intermetal oxygen atom transfer and nuclear magnetic resonance studies
Templeton, Joseph L.,Ward, Bennett C.,Chen, Grace J.-J.,McDonald, John W.,Newton, William E.
, p. 1248 - 1253 (1981)
The first synthesis of oxotungsten(IV)-acetylene complexes, OW(R1C≡CR2)(S2CNR2) 2, has been effected by controlled oxidation of W(CO)(R1C≡CR2)(S2CNR2) 2 with the dimeric oxygen atom transfer reagent Mo2O3[S2P(OEt)2]4. These complexes, including the parent C2H2 derivative, are stable toward alkyne dissociation (cf. OMo(HC2H)(S2CNR2)2) and have been characterized by elemental analysis, infrared spectroscopy, and variable-temperature nuclear magnetic resonance techniques. Dynamic NMR studies support the premise that a single molecular process is responsible for coalescence of the acetylenic proton signals and the dithiocarbamate alkyl signals. Neither acetylene rotation nor rotation around the C-N bond of the dithiocarbamate ligands is adequate to account for the experimental observations. A rearrangement of the chelating ligands, perhaps via dissociation of the sulfur trans to oxygen to form a fluxional five-coordinate intermediate, is compatible with the data obtained for OW(C2H2)(S2CNEt2)2, OW(C2H2)(S2CNMe2)2, and OW(PhC2H)(S2CNMe2)2.
