Characterization of reactions of hydrogen with coordinated sulfido ligands

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

Research output: Contribution to journalArticle

191 Citations (Scopus)

Abstract

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
Volume102
Issue number25
Publication statusPublished - 1980

Fingerprint

Sulfur
Hydrogen
Ligands
Derivatives
Hydrogen Sulfide
Hydrogen sulfide
Acetylene
Atoms
Hydrodesulfurization
Carbon Monoxide
X-Ray Diffraction
Isomers
Metal ions
Ethylene
Metals
Single crystals
Ions
X ray diffraction
Catalysts

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Rakowski DuBois, M., VanDerveer, M. C., DuBois, D. L., Haltiwanger, R. C., & Miller, W. K. (1980). Characterization of reactions of hydrogen with coordinated sulfido ligands. Journal of the American Chemical Society, 102(25), 7456-7461.

Characterization of reactions of hydrogen with coordinated sulfido ligands. / Rakowski DuBois, M.; VanDerveer, M. C.; DuBois, Daniel L; Haltiwanger, R. C.; Miller, W. K.

In: Journal of the American Chemical Society, Vol. 102, No. 25, 1980, p. 7456-7461.

Research output: Contribution to journalArticle

Rakowski DuBois, M, VanDerveer, MC, DuBois, DL, Haltiwanger, RC & Miller, WK 1980, 'Characterization of reactions of hydrogen with coordinated sulfido ligands', Journal of the American Chemical Society, vol. 102, no. 25, pp. 7456-7461.
Rakowski DuBois M, VanDerveer MC, DuBois DL, Haltiwanger RC, Miller WK. Characterization of reactions of hydrogen with coordinated sulfido ligands. Journal of the American Chemical Society. 1980;102(25):7456-7461.
Rakowski DuBois, M. ; VanDerveer, M. C. ; DuBois, Daniel L ; Haltiwanger, R. C. ; Miller, W. K. / Characterization of reactions of hydrogen with coordinated sulfido ligands. In: Journal of the American Chemical Society. 1980 ; Vol. 102, No. 25. pp. 7456-7461.
@article{be92c3f8aba84aea81f19233d6a7509c,
title = "Characterization of reactions of hydrogen with coordinated sulfido ligands",
abstract = "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) {\AA}, b = 14.184 (7) {\AA}, c = 7.805 (2) {\AA}, 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.",
author = "{Rakowski DuBois}, M. and VanDerveer, {M. C.} and DuBois, {Daniel L} and Haltiwanger, {R. C.} and Miller, {W. K.}",
year = "1980",
language = "English",
volume = "102",
pages = "7456--7461",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "25",

}

TY - JOUR

T1 - Characterization of reactions of hydrogen with coordinated sulfido ligands

AU - Rakowski DuBois, M.

AU - VanDerveer, M. C.

AU - DuBois, Daniel L

AU - Haltiwanger, R. C.

AU - Miller, W. K.

PY - 1980

Y1 - 1980

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=33847086984&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33847086984&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:33847086984

VL - 102

SP - 7456

EP - 7461

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 25

ER -