# 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.

## BibTeX

@article{Adams:2004:NMC,
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.