New disulfido molybdenum-manganese complexes exhibit facile addition of small molecules to the sulfur atoms

Richard D. Adams, Burjor Captain, O. Sung Kwon, Shaobin Miao

Research output: Contribution to journalArticle

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Abstract

The reaction of Mn2(CO)7(μ-S2) (1) with [CpMo(CO)3]2 (Cp = C5H5) and [Cp*Mo(CO)3]2 (Cp* = C5(CH3)5) yielded the new mixed-metal disulfide complexes CpMoMn(CO)5(μ-S2) (2) and Cp*MoMn(CO)5(μ-S2) (3) by a metal-metal exchange reaction. Compounds 2 and 3 both contain a bridging disulfido ligand lying perpendicular to the Mo-Mn bond. The bond distances are Mo-Mn = 2.8421(10) and 2.8914(5) Å and S-S = 2.042(2) and 1.9973(10) Å for 2 and 3, respectively. A tetranuclear metal side product CpMoMn3(CO)133-S)(μ4-S) (4) was also isolated from the reaction of 1 with [CpMo(CO)3]2. Compounds 2 and 3 react with CO to yield the dithiocarbonato complexes CpMoMn- (CO)5[μ-SC(=O)S] (5) and Cp*MoMn(CO)5[μ-SC(=O)S] (6) by insertion of CO into the S-S bond. Similarly, tert-butylisocyanide was inserted into the S-S bond of 2 and 3 to yield the complexes CpMoMn(CO)5[μ-S(C=NBut)S] (7) and Cp*MoMn(CO)5[μ-S(C=NBut)S] (8), respectively. Ethylene and dimethylacetylene dicarboxylate also inserted into the S-S bond of 2 and 3 at room temperature to yield the ethanedithiolato ligand bridged complexes CpMoMn- (CO)5(μ-SCH2CH2S) (9), Cp*MoMn(CO)5(μ-SCH2CH2S) (10), CpMoMn(CO)5[μ-SC(CO2Me)=C(CO2Me)S] (11), and Cp*MoMn(CO)5[μ-SC(CO2Me)=C(CO2Me)S] (12). Allene was found to insert into the S-S bond of 2 by using one of its two double bonds to yield the complex CpMoMn(CO)5[μ-SCH2C(=CH2)S] (13). The molecular structures of the new complexes 2-7 and 9-13 were established by single-crystal X-ray diffraction analyses.

Original languageEnglish
Pages (from-to)3356-3365
Number of pages10
JournalInorganic Chemistry
Volume42
Issue number10
DOIs
StatePublished - May 19 2003
Externally publishedYes

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Molybdenum
Manganese
Sulfur
molybdenum
manganese
sulfur
Metals
Atoms
Molecules
metals
atoms
molecules
Ligands
ligands
disulfides
inserts
Disulfides
Molecular structure
insertion
ethylene

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

New disulfido molybdenum-manganese complexes exhibit facile addition of small molecules to the sulfur atoms. / Adams, Richard D.; Captain, Burjor; Kwon, O. Sung; Miao, Shaobin.

In: Inorganic Chemistry, Vol. 42, No. 10, 19.05.2003, p. 3356-3365.

Research output: Contribution to journalArticle

Adams, Richard D. ; Captain, Burjor ; Kwon, O. Sung ; Miao, Shaobin. / New disulfido molybdenum-manganese complexes exhibit facile addition of small molecules to the sulfur atoms. In: Inorganic Chemistry. 2003 ; Vol. 42, No. 10. pp. 3356-3365.
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title = "New disulfido molybdenum-manganese complexes exhibit facile addition of small molecules to the sulfur atoms",
abstract = "The reaction of Mn2(CO)7(μ-S2) (1) with [CpMo(CO)3]2 (Cp = C5H5) and [Cp*Mo(CO)3]2 (Cp* = C5(CH3)5) yielded the new mixed-metal disulfide complexes CpMoMn(CO)5(μ-S2) (2) and Cp*MoMn(CO)5(μ-S2) (3) by a metal-metal exchange reaction. Compounds 2 and 3 both contain a bridging disulfido ligand lying perpendicular to the Mo-Mn bond. The bond distances are Mo-Mn = 2.8421(10) and 2.8914(5) {\AA} and S-S = 2.042(2) and 1.9973(10) {\AA} for 2 and 3, respectively. A tetranuclear metal side product CpMoMn3(CO)13(μ3-S)(μ4-S) (4) was also isolated from the reaction of 1 with [CpMo(CO)3]2. Compounds 2 and 3 react with CO to yield the dithiocarbonato complexes CpMoMn- (CO)5[μ-SC(=O)S] (5) and Cp*MoMn(CO)5[μ-SC(=O)S] (6) by insertion of CO into the S-S bond. Similarly, tert-butylisocyanide was inserted into the S-S bond of 2 and 3 to yield the complexes CpMoMn(CO)5[μ-S(C=NBut)S] (7) and Cp*MoMn(CO)5[μ-S(C=NBut)S] (8), respectively. Ethylene and dimethylacetylene dicarboxylate also inserted into the S-S bond of 2 and 3 at room temperature to yield the ethanedithiolato ligand bridged complexes CpMoMn- (CO)5(μ-SCH2CH2S) (9), Cp*MoMn(CO)5(μ-SCH2CH2S) (10), CpMoMn(CO)5[μ-SC(CO2Me)=C(CO2Me)S] (11), and Cp*MoMn(CO)5[μ-SC(CO2Me)=C(CO2Me)S] (12). Allene was found to insert into the S-S bond of 2 by using one of its two double bonds to yield the complex CpMoMn(CO)5[μ-SCH2C(=CH2)S] (13). The molecular structures of the new complexes 2-7 and 9-13 were established by single-crystal X-ray diffraction analyses.",
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T1 - New disulfido molybdenum-manganese complexes exhibit facile addition of small molecules to the sulfur atoms

AU - Adams, Richard D.

AU - Captain, Burjor

AU - Kwon, O. Sung

AU - Miao, Shaobin

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N2 - The reaction of Mn2(CO)7(μ-S2) (1) with [CpMo(CO)3]2 (Cp = C5H5) and [Cp*Mo(CO)3]2 (Cp* = C5(CH3)5) yielded the new mixed-metal disulfide complexes CpMoMn(CO)5(μ-S2) (2) and Cp*MoMn(CO)5(μ-S2) (3) by a metal-metal exchange reaction. Compounds 2 and 3 both contain a bridging disulfido ligand lying perpendicular to the Mo-Mn bond. The bond distances are Mo-Mn = 2.8421(10) and 2.8914(5) Å and S-S = 2.042(2) and 1.9973(10) Å for 2 and 3, respectively. A tetranuclear metal side product CpMoMn3(CO)13(μ3-S)(μ4-S) (4) was also isolated from the reaction of 1 with [CpMo(CO)3]2. Compounds 2 and 3 react with CO to yield the dithiocarbonato complexes CpMoMn- (CO)5[μ-SC(=O)S] (5) and Cp*MoMn(CO)5[μ-SC(=O)S] (6) by insertion of CO into the S-S bond. Similarly, tert-butylisocyanide was inserted into the S-S bond of 2 and 3 to yield the complexes CpMoMn(CO)5[μ-S(C=NBut)S] (7) and Cp*MoMn(CO)5[μ-S(C=NBut)S] (8), respectively. Ethylene and dimethylacetylene dicarboxylate also inserted into the S-S bond of 2 and 3 at room temperature to yield the ethanedithiolato ligand bridged complexes CpMoMn- (CO)5(μ-SCH2CH2S) (9), Cp*MoMn(CO)5(μ-SCH2CH2S) (10), CpMoMn(CO)5[μ-SC(CO2Me)=C(CO2Me)S] (11), and Cp*MoMn(CO)5[μ-SC(CO2Me)=C(CO2Me)S] (12). Allene was found to insert into the S-S bond of 2 by using one of its two double bonds to yield the complex CpMoMn(CO)5[μ-SCH2C(=CH2)S] (13). The molecular structures of the new complexes 2-7 and 9-13 were established by single-crystal X-ray diffraction analyses.

AB - The reaction of Mn2(CO)7(μ-S2) (1) with [CpMo(CO)3]2 (Cp = C5H5) and [Cp*Mo(CO)3]2 (Cp* = C5(CH3)5) yielded the new mixed-metal disulfide complexes CpMoMn(CO)5(μ-S2) (2) and Cp*MoMn(CO)5(μ-S2) (3) by a metal-metal exchange reaction. Compounds 2 and 3 both contain a bridging disulfido ligand lying perpendicular to the Mo-Mn bond. The bond distances are Mo-Mn = 2.8421(10) and 2.8914(5) Å and S-S = 2.042(2) and 1.9973(10) Å for 2 and 3, respectively. A tetranuclear metal side product CpMoMn3(CO)13(μ3-S)(μ4-S) (4) was also isolated from the reaction of 1 with [CpMo(CO)3]2. Compounds 2 and 3 react with CO to yield the dithiocarbonato complexes CpMoMn- (CO)5[μ-SC(=O)S] (5) and Cp*MoMn(CO)5[μ-SC(=O)S] (6) by insertion of CO into the S-S bond. Similarly, tert-butylisocyanide was inserted into the S-S bond of 2 and 3 to yield the complexes CpMoMn(CO)5[μ-S(C=NBut)S] (7) and Cp*MoMn(CO)5[μ-S(C=NBut)S] (8), respectively. Ethylene and dimethylacetylene dicarboxylate also inserted into the S-S bond of 2 and 3 at room temperature to yield the ethanedithiolato ligand bridged complexes CpMoMn- (CO)5(μ-SCH2CH2S) (9), Cp*MoMn(CO)5(μ-SCH2CH2S) (10), CpMoMn(CO)5[μ-SC(CO2Me)=C(CO2Me)S] (11), and Cp*MoMn(CO)5[μ-SC(CO2Me)=C(CO2Me)S] (12). Allene was found to insert into the S-S bond of 2 by using one of its two double bonds to yield the complex CpMoMn(CO)5[μ-SCH2C(=CH2)S] (13). The molecular structures of the new complexes 2-7 and 9-13 were established by single-crystal X-ray diffraction analyses.

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