Characterization of reactions of hydrogen with coordinated sulfido ligands

M. Rakowski DuBois, M. C. VanDerveer, Daniel L DuBois, R. C. Haltiwanger, W. K. Miller

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196 Citations (Scopus)


Complexes of the formula [(CH3)nC5H5-nMo(S)SH]2, where n = 0, 1, and 5, have been prepared by the reaction of hydrogen with several different cyclopentadienylmolybdenum derivatives containing sulfido ligands. These include the insoluble polymeric products [MenCpMoSx]y, resulting from the reaction of elemental sulfur with [MenCpMo(CO)3]2. Excess sulfur in these species is converted to hydrogen sulfide during the course of the reaction with hydrogen. The hydrosulfido complexes have been characterized by spectral methods, and several reactions of these complexes have been studied. The complex [MeCpMo(S)SH]2 catalyzes HD exchange between H2 and D2 as well as between H2 and D2O. The reduction of elemental sulfur to hydrogen sulfide by H2 is catalyzed by the SH complexes under mild homogeneous conditions. Ethylene and acetylene react with the complexes to displace hydrogen from the SH ligands and form derivatives with bridging dithiolate ligands. Alkyl-and arylthiols react with the SH complexes to form H2S and derivatives of the formula [MenCpMo(S)SR]2 where R = CH3, C2H5, i-C3H7, and C6H5. Spectral data suggest that these complexes have the same gross structures as the SH compounds. A single crystal of the derivative with n = 1 and R = CH3 has been characterized by an X-ray diffraction study. The compound crystallizes in the space group P21/c with the cell dimensions a = 7.794 (3) Å, b = 14.184 (7) Å, c = 7.805 (2) Å, and β = 100.03 (3)°. All four sulfur atoms in the complex occupy positions bridging the two metal ions. The S-methyl groups are oriented on trans sulfur atoms so as to form a centrosymmetric isomer. The relationship between the chemistry of these new complexes and aspects of proposed mechanisms of the hydrodesulfurization catalysts are discussed.

Original languageEnglish
Pages (from-to)7456-7461
Number of pages6
JournalJournal of the American Chemical Society
Issue number25
Publication statusPublished - 1980

ASJC Scopus subject areas

  • Chemistry(all)

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