Syntheses, structures, and reactions of molybdenum complexes with sulfido and disulfido ligands

M. Rakowski Dubois, Daniel L DuBois, M. C. Vanderveer, R. C. Haltiwanger

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Abstract

The reaction of elemental sulfur with (CH3)5C5Mo(CO)3H produced [(CH3)5C5MoS2]2 (II) and [(CH3)5C5MoS5]2 (IV) in 65% and 10% yields, respectively. The remaining product was an insoluble, presumably polymeric, material. Complex II crystallizes in space group P21/n with a = 10.069 (20) Å, b = 15.107 (4) Å, c = 7.889 (2) Å, and β = 104.81 (2)°. The molecule contains a planar Mo2(μ-S)2 unit with terminal sulfido ligands in the anti configuration. In the presence of oxygen, complex II is converted to [(CH3)5C5MoO(S)]2, which crystallizes in space group P42/n with a = b= 16.342 (3) Å and c = 8.456 (1) Å. The molecule is similar to complex II with oxo ligands replacing the terminal sulfido ligands. Complex IV crystallizes in space group Fdd2 with a = 15.233 (3) Å, b = 45.205 (7) Å, and c = 8.051 (2) Å. The metal ions in this dimer are each coordinated to a single sulfur atom of a bridging disulfide ligand. The coordination sphere of each molybdenum ion also includes two η2-S2 ligands and the η5-(CH3)5C5 ligand. The reactions of [CH3C5H4Mo(CO)3]2 and of [C5H5Mo(CO)3]2 with elemental sulfur resulted primarily in the formation of insoluble materials. The dimer [CH3C5H4MoS2]2 (III) was isolated from the former reaction in very low yields. An X-ray diffraction study of this product confirms that it is also an anti isomer of a [MoS(μ-S)]2 dimer. The complex crystallizes in space group P21/n with a = 7.023 (4) Å, b = 6.703 (2) Å, c = 16.227 (8) Å, and β = 95.86 (4)°. Complexes II-IV, as well as the insoluble products from these reactions, react with hydrogen under mild conditions to form in each case a complex with bydrosulfido ligands. In addition, III reacts with ethylene and acetylene at room temperature to form the known dimers with bridging ethane-and ethenedithiolate ligands, respectively. The insoluble materials [(CH3)nC5H5-nMoSx] y (n = 1, 5) also react with these unsaturated hydrocarbons to form the same dithiolate-bridged dimers.

Original languageEnglish
Pages (from-to)3064-3071
Number of pages8
JournalInorganic Chemistry
Volume20
Issue number9
Publication statusPublished - 1981

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Molybdenum
molybdenum
Ligands
ligands
Dimers
synthesis
dimers
Sulfur
sulfur
products
Acetylene
Molecules
Ethane
disulfides
Hydrocarbons
acetylene
Disulfides
Isomers
ethane
Metal ions

ASJC Scopus subject areas

  • Inorganic Chemistry

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Syntheses, structures, and reactions of molybdenum complexes with sulfido and disulfido ligands. / Dubois, M. Rakowski; DuBois, Daniel L; Vanderveer, M. C.; Haltiwanger, R. C.

In: Inorganic Chemistry, Vol. 20, No. 9, 1981, p. 3064-3071.

Research output: Contribution to journalArticle

Dubois, MR, DuBois, DL, Vanderveer, MC & Haltiwanger, RC 1981, 'Syntheses, structures, and reactions of molybdenum complexes with sulfido and disulfido ligands', Inorganic Chemistry, vol. 20, no. 9, pp. 3064-3071.
Dubois, M. Rakowski ; DuBois, Daniel L ; Vanderveer, M. C. ; Haltiwanger, R. C. / Syntheses, structures, and reactions of molybdenum complexes with sulfido and disulfido ligands. In: Inorganic Chemistry. 1981 ; Vol. 20, No. 9. pp. 3064-3071.
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title = "Syntheses, structures, and reactions of molybdenum complexes with sulfido and disulfido ligands",
abstract = "The reaction of elemental sulfur with (CH3)5C5Mo(CO)3H produced [(CH3)5C5MoS2]2 (II) and [(CH3)5C5MoS5]2 (IV) in 65{\%} and 10{\%} yields, respectively. The remaining product was an insoluble, presumably polymeric, material. Complex II crystallizes in space group P21/n with a = 10.069 (20) {\AA}, b = 15.107 (4) {\AA}, c = 7.889 (2) {\AA}, and β = 104.81 (2)°. The molecule contains a planar Mo2(μ-S)2 unit with terminal sulfido ligands in the anti configuration. In the presence of oxygen, complex II is converted to [(CH3)5C5MoO(S)]2, which crystallizes in space group P42/n with a = b= 16.342 (3) {\AA} and c = 8.456 (1) {\AA}. The molecule is similar to complex II with oxo ligands replacing the terminal sulfido ligands. Complex IV crystallizes in space group Fdd2 with a = 15.233 (3) {\AA}, b = 45.205 (7) {\AA}, and c = 8.051 (2) {\AA}. The metal ions in this dimer are each coordinated to a single sulfur atom of a bridging disulfide ligand. The coordination sphere of each molybdenum ion also includes two η2-S2 ligands and the η5-(CH3)5C5 ligand. The reactions of [CH3C5H4Mo(CO)3]2 and of [C5H5Mo(CO)3]2 with elemental sulfur resulted primarily in the formation of insoluble materials. The dimer [CH3C5H4MoS2]2 (III) was isolated from the former reaction in very low yields. An X-ray diffraction study of this product confirms that it is also an anti isomer of a [MoS(μ-S)]2 dimer. The complex crystallizes in space group P21/n with a = 7.023 (4) {\AA}, b = 6.703 (2) {\AA}, c = 16.227 (8) {\AA}, and β = 95.86 (4)°. Complexes II-IV, as well as the insoluble products from these reactions, react with hydrogen under mild conditions to form in each case a complex with bydrosulfido ligands. In addition, III reacts with ethylene and acetylene at room temperature to form the known dimers with bridging ethane-and ethenedithiolate ligands, respectively. The insoluble materials [(CH3)nC5H5-nMoSx] y (n = 1, 5) also react with these unsaturated hydrocarbons to form the same dithiolate-bridged dimers.",
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T1 - Syntheses, structures, and reactions of molybdenum complexes with sulfido and disulfido ligands

AU - Dubois, M. Rakowski

AU - DuBois, Daniel L

AU - Vanderveer, M. C.

AU - Haltiwanger, R. C.

PY - 1981

Y1 - 1981

N2 - The reaction of elemental sulfur with (CH3)5C5Mo(CO)3H produced [(CH3)5C5MoS2]2 (II) and [(CH3)5C5MoS5]2 (IV) in 65% and 10% yields, respectively. The remaining product was an insoluble, presumably polymeric, material. Complex II crystallizes in space group P21/n with a = 10.069 (20) Å, b = 15.107 (4) Å, c = 7.889 (2) Å, and β = 104.81 (2)°. The molecule contains a planar Mo2(μ-S)2 unit with terminal sulfido ligands in the anti configuration. In the presence of oxygen, complex II is converted to [(CH3)5C5MoO(S)]2, which crystallizes in space group P42/n with a = b= 16.342 (3) Å and c = 8.456 (1) Å. The molecule is similar to complex II with oxo ligands replacing the terminal sulfido ligands. Complex IV crystallizes in space group Fdd2 with a = 15.233 (3) Å, b = 45.205 (7) Å, and c = 8.051 (2) Å. The metal ions in this dimer are each coordinated to a single sulfur atom of a bridging disulfide ligand. The coordination sphere of each molybdenum ion also includes two η2-S2 ligands and the η5-(CH3)5C5 ligand. The reactions of [CH3C5H4Mo(CO)3]2 and of [C5H5Mo(CO)3]2 with elemental sulfur resulted primarily in the formation of insoluble materials. The dimer [CH3C5H4MoS2]2 (III) was isolated from the former reaction in very low yields. An X-ray diffraction study of this product confirms that it is also an anti isomer of a [MoS(μ-S)]2 dimer. The complex crystallizes in space group P21/n with a = 7.023 (4) Å, b = 6.703 (2) Å, c = 16.227 (8) Å, and β = 95.86 (4)°. Complexes II-IV, as well as the insoluble products from these reactions, react with hydrogen under mild conditions to form in each case a complex with bydrosulfido ligands. In addition, III reacts with ethylene and acetylene at room temperature to form the known dimers with bridging ethane-and ethenedithiolate ligands, respectively. The insoluble materials [(CH3)nC5H5-nMoSx] y (n = 1, 5) also react with these unsaturated hydrocarbons to form the same dithiolate-bridged dimers.

AB - The reaction of elemental sulfur with (CH3)5C5Mo(CO)3H produced [(CH3)5C5MoS2]2 (II) and [(CH3)5C5MoS5]2 (IV) in 65% and 10% yields, respectively. The remaining product was an insoluble, presumably polymeric, material. Complex II crystallizes in space group P21/n with a = 10.069 (20) Å, b = 15.107 (4) Å, c = 7.889 (2) Å, and β = 104.81 (2)°. The molecule contains a planar Mo2(μ-S)2 unit with terminal sulfido ligands in the anti configuration. In the presence of oxygen, complex II is converted to [(CH3)5C5MoO(S)]2, which crystallizes in space group P42/n with a = b= 16.342 (3) Å and c = 8.456 (1) Å. The molecule is similar to complex II with oxo ligands replacing the terminal sulfido ligands. Complex IV crystallizes in space group Fdd2 with a = 15.233 (3) Å, b = 45.205 (7) Å, and c = 8.051 (2) Å. The metal ions in this dimer are each coordinated to a single sulfur atom of a bridging disulfide ligand. The coordination sphere of each molybdenum ion also includes two η2-S2 ligands and the η5-(CH3)5C5 ligand. The reactions of [CH3C5H4Mo(CO)3]2 and of [C5H5Mo(CO)3]2 with elemental sulfur resulted primarily in the formation of insoluble materials. The dimer [CH3C5H4MoS2]2 (III) was isolated from the former reaction in very low yields. An X-ray diffraction study of this product confirms that it is also an anti isomer of a [MoS(μ-S)]2 dimer. The complex crystallizes in space group P21/n with a = 7.023 (4) Å, b = 6.703 (2) Å, c = 16.227 (8) Å, and β = 95.86 (4)°. Complexes II-IV, as well as the insoluble products from these reactions, react with hydrogen under mild conditions to form in each case a complex with bydrosulfido ligands. In addition, III reacts with ethylene and acetylene at room temperature to form the known dimers with bridging ethane-and ethenedithiolate ligands, respectively. The insoluble materials [(CH3)nC5H5-nMoSx] y (n = 1, 5) also react with these unsaturated hydrocarbons to form the same dithiolate-bridged dimers.

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