Nickel-Manganese Sulfido Carbonyl Cluster Complexes. Synthesis, Structure, and Properties of the Unusual Paramagnetic Complexes Cp2Ni 2Mn(CO)33-E)2, E = S, Se

Richard D. Adams, Shaobin Miao, Mark D. Smith, Horatio Farach, Charles Edwin Webster, Josiah Manson, Michael B. Hall

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Abstract

The reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 yielded the paramagnetic new compound Cp 2Ni2Mn(CO)33-S)2 (1) and a new hexanuclear metal product Cp2Ni2Mn 4(CO)146-S2)(μ 3-S)2 (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni2Mn triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements of 1 show that it contains one unpaired electron. The electronic structure of 1 was determined by Fenske-Hall molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital delocalized unequally across the three metal atoms. The selenium homologue Cp2Ni2Mn(CO)33-Se)2 (3) was obtained from the reaction of a mixture of Mn2(CO) 10 and [CpNi(CO)]2 with elemental selenium and Me 3NO·2H2O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp2Ni2Mn 2(CO)64-S2)(μ 4-S5), 4, which can also be made from the reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 and sulfur. Compound 4 was converted back to 1 by sulfur abstraction using PPh3. The reaction of Mn2(CO)10 with [CpNi(CO)]2 in the presence of thiirane yielded the ethanedithiolato compound CpNiMn(CO)3(μ-SCH2CH2S) (5), which was also obtained from the reaction of Mn4(CO)153-S2)(μ4-S2) with [CpNi-(CO)]2 in the presence of thiirane. Compound 5 reacted with additional quantities of thiirane to yield the new compound CpNiMn(CO) 3[μ-S(CH2CH2S)2], 6, which contains a 3-thiapentanedithiolato ligand that bridges the two metal atoms. Compound 6 was also obtained from the reaction of Mn2(CO) 10 with CpNi(CO)12 and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses.

Original languageEnglish (US)
Pages (from-to)2515-2525
Number of pages11
JournalInorganic Chemistry
Volume43
Issue number8
DOIs
StatePublished - Apr 19 2004

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Manganese
Nickel
manganese
Sulfur
nickel
Metals
synthesis
Selenium
Electrons
sulfur
Ligands
selenium
Orbital calculations
Atoms
Molecular orbitals
Magnetic susceptibility
metals
Molecular structure
Electronic structure
Paramagnetic resonance

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Nickel-Manganese Sulfido Carbonyl Cluster Complexes. Synthesis, Structure, and Properties of the Unusual Paramagnetic Complexes Cp2Ni 2Mn(CO)33-E)2, E = S, Se. / Adams, Richard D.; Miao, Shaobin; Smith, Mark D.; Farach, Horatio; Webster, Charles Edwin; Manson, Josiah; Hall, Michael B.

In: Inorganic Chemistry, Vol. 43, No. 8, 19.04.2004, p. 2515-2525.

Research output: Contribution to journalArticle

Adams, Richard D. ; Miao, Shaobin ; Smith, Mark D. ; Farach, Horatio ; Webster, Charles Edwin ; Manson, Josiah ; Hall, Michael B. / Nickel-Manganese Sulfido Carbonyl Cluster Complexes. Synthesis, Structure, and Properties of the Unusual Paramagnetic Complexes Cp2Ni 2Mn(CO)33-E)2, E = S, Se. In: Inorganic Chemistry. 2004 ; Vol. 43, No. 8. pp. 2515-2525.
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title = "Nickel-Manganese Sulfido Carbonyl Cluster Complexes. Synthesis, Structure, and Properties of the Unusual Paramagnetic Complexes Cp2Ni 2Mn(CO)3(μ3-E)2, E = S, Se",
abstract = "The reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 yielded the paramagnetic new compound Cp 2Ni2Mn(CO)3(μ3-S)2 (1) and a new hexanuclear metal product Cp2Ni2Mn 4(CO)14(μ6-S2)(μ 3-S)2 (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni2Mn triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements of 1 show that it contains one unpaired electron. The electronic structure of 1 was determined by Fenske-Hall molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital delocalized unequally across the three metal atoms. The selenium homologue Cp2Ni2Mn(CO)3(μ3-Se)2 (3) was obtained from the reaction of a mixture of Mn2(CO) 10 and [CpNi(CO)]2 with elemental selenium and Me 3NO·2H2O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp2Ni2Mn 2(CO)6(μ4-S2)(μ 4-S5), 4, which can also be made from the reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 and sulfur. Compound 4 was converted back to 1 by sulfur abstraction using PPh3. The reaction of Mn2(CO)10 with [CpNi(CO)]2 in the presence of thiirane yielded the ethanedithiolato compound CpNiMn(CO)3(μ-SCH2CH2S) (5), which was also obtained from the reaction of Mn4(CO)15(μ 3-S2)(μ4-S2) with [CpNi-(CO)]2 in the presence of thiirane. Compound 5 reacted with additional quantities of thiirane to yield the new compound CpNiMn(CO) 3[μ-S(CH2CH2S)2], 6, which contains a 3-thiapentanedithiolato ligand that bridges the two metal atoms. Compound 6 was also obtained from the reaction of Mn2(CO) 10 with CpNi(CO)12 and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses.",
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T1 - Nickel-Manganese Sulfido Carbonyl Cluster Complexes. Synthesis, Structure, and Properties of the Unusual Paramagnetic Complexes Cp2Ni 2Mn(CO)3(μ3-E)2, E = S, Se

AU - Adams, Richard D.

AU - Miao, Shaobin

AU - Smith, Mark D.

AU - Farach, Horatio

AU - Webster, Charles Edwin

AU - Manson, Josiah

AU - Hall, Michael B.

PY - 2004/4/19

Y1 - 2004/4/19

N2 - The reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 yielded the paramagnetic new compound Cp 2Ni2Mn(CO)3(μ3-S)2 (1) and a new hexanuclear metal product Cp2Ni2Mn 4(CO)14(μ6-S2)(μ 3-S)2 (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni2Mn triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements of 1 show that it contains one unpaired electron. The electronic structure of 1 was determined by Fenske-Hall molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital delocalized unequally across the three metal atoms. The selenium homologue Cp2Ni2Mn(CO)3(μ3-Se)2 (3) was obtained from the reaction of a mixture of Mn2(CO) 10 and [CpNi(CO)]2 with elemental selenium and Me 3NO·2H2O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp2Ni2Mn 2(CO)6(μ4-S2)(μ 4-S5), 4, which can also be made from the reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 and sulfur. Compound 4 was converted back to 1 by sulfur abstraction using PPh3. The reaction of Mn2(CO)10 with [CpNi(CO)]2 in the presence of thiirane yielded the ethanedithiolato compound CpNiMn(CO)3(μ-SCH2CH2S) (5), which was also obtained from the reaction of Mn4(CO)15(μ 3-S2)(μ4-S2) with [CpNi-(CO)]2 in the presence of thiirane. Compound 5 reacted with additional quantities of thiirane to yield the new compound CpNiMn(CO) 3[μ-S(CH2CH2S)2], 6, which contains a 3-thiapentanedithiolato ligand that bridges the two metal atoms. Compound 6 was also obtained from the reaction of Mn2(CO) 10 with CpNi(CO)12 and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses.

AB - The reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 yielded the paramagnetic new compound Cp 2Ni2Mn(CO)3(μ3-S)2 (1) and a new hexanuclear metal product Cp2Ni2Mn 4(CO)14(μ6-S2)(μ 3-S)2 (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni2Mn triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements of 1 show that it contains one unpaired electron. The electronic structure of 1 was determined by Fenske-Hall molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital delocalized unequally across the three metal atoms. The selenium homologue Cp2Ni2Mn(CO)3(μ3-Se)2 (3) was obtained from the reaction of a mixture of Mn2(CO) 10 and [CpNi(CO)]2 with elemental selenium and Me 3NO·2H2O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp2Ni2Mn 2(CO)6(μ4-S2)(μ 4-S5), 4, which can also be made from the reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 and sulfur. Compound 4 was converted back to 1 by sulfur abstraction using PPh3. The reaction of Mn2(CO)10 with [CpNi(CO)]2 in the presence of thiirane yielded the ethanedithiolato compound CpNiMn(CO)3(μ-SCH2CH2S) (5), which was also obtained from the reaction of Mn4(CO)15(μ 3-S2)(μ4-S2) with [CpNi-(CO)]2 in the presence of thiirane. Compound 5 reacted with additional quantities of thiirane to yield the new compound CpNiMn(CO) 3[μ-S(CH2CH2S)2], 6, which contains a 3-thiapentanedithiolato ligand that bridges the two metal atoms. Compound 6 was also obtained from the reaction of Mn2(CO) 10 with CpNi(CO)12 and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses.

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