Nickel-Manganese Sulfido Carbonyl Cluster Complexes. Synthesis, Structure, and Properties of the Unusual Paramagnetic Complexes Cp₂Ni₂Mn(CO)₃(μ₃-E)₂, E = S, Se

We investigate the synthesis, structure, and properties of Nickel-Manganese complexes. These complexes have potential applications as catalysts for removing sulfur from gasoline.

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BibTeX

@article{Adams:2004:NMC,
  author  = {Richard Adams and
             Shaobin Miao and
             Mark Smith and
             Horatio Farach and
             Charles Webster and
             Josiah Manson and
             Michael Hall},
  title   = {Nickel-Manganese Sulfido Carbonyl Cluster Complexes. 
             Synthesis, Structure, and Properties of the Unusual 
             Paramagnetic Complexes Cp_2Ni_2Mn(CO)_3(\mu_3-E)_2, 
             E = S, Se},
  journal = {Inorganic Chemistry},
  year    = {2004},
}

Abstract

The reaction of Mn2(CO)7(-S2) with [CpNi(CO)]2 yielded the paramagnetic new compound Cp2Ni2Mn(CO)3(3-S)2 (1) and a new hexanuclear metal product Cp2Ni2Mn4(CO)14(6-S2)(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(3-Se)2 (3) was obtained from the reaction of a mixture of Mn2(CO)10 and [CpNi(CO)]2 with elemental selenium and Me3NO·2H2O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp2Ni2Mn2(CO)6(4-S2)(4-S5), 4, which can also be made from the reaction of Mn2(CO)7(-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(-SCH2CH2S) (5), which was also obtained from the reaction of Mn4(CO)15(3-S2)(4-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[-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)]2 and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses.

License

The images, executables, and code supplied are from the web page http://josiahmanson.com. These materials are free to use for non-commercial purposes. Any works that use materials from this web page should acknowledge Josiah Manson and the paper Nickel-Manganese Sulfido Carbonyl Cluster Complexes. Synthesis, Structure, and Properties of the Unusual Paramagnetic Complexes Cp₂Ni₂Mn(CO)₃(μ₃-E)₂, E = S, Se. For commercial use, please contact Josiah Manson (josiahmanson@gmail.com).