ArticleInorganic chemistry2011
The [MoFe3S4]2+ oxidation state: synthesis, substitution reactions, and structures of phosphine-ligated cubane-type clusters with the S=2 ground state.
Article in Inorganic chemistry, 2011. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 5 papers.
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5 citing papers in PubMed.
- Molybdenum doping enhances backbonding at neighboring iron centers in iron-sulfur clusters.Chem · 2026Article
- Dinitrogen binding and activation at a molybdenum-iron-sulfur cluster.Nature chemistry · 2021Article
- Selenium as a structural surrogate of sulfur: template-assisted assembly of five types of tungsten-iron-sulfur/selenium clusters and the structural fate of chalcogenide reactants.Journal of the American Chemical Society · 2012Article
- Cubane-type Fe4S4 clusters with chiral thiolate ligation: formation by ligand substitution, detection of intermediates by 1H NMR, and solid state structures including spontaneous resolution upon crystallization.Inorganic chemistry · 2011Article
- Specific incorporation of chalcogenide bridge atoms in molybdenum/tungsten-iron-sulfur single cubane clusters.Inorganic chemistry · 2011Article
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Abstract
The cluster [(Tp)MoFe(3)S(4)(PEt(3))(3)](1+) containing the cubane-type [MoFe(3)(μ(3)-S)(4)](2+) reduced core undergoes facile ligand substitution reactions at the iron sites leading to an extensive set of mono- and disubstituted species [(Tp)MoFe(3)S(4)(PEt(3))(3-n)L(n)](1-n) with L = halide, N(3)(-), PhS(-), PhSe(-), R(3)SiO(-), and R(3)SiS(-) and n = 1 and 2. Structures of 10 members of the set are reported. For two representative clusters, Curie behavior at 2-20 K indicates a spin-quintet ground state. Zero-field Mössbauer spectra consist of two doublets in a 2:1 intensity ratio. (57)Fe isomer shifts are consistent with the mean oxidation state Fe(3)(2.33+) arising from electron delocalization of the mixed-valence oxidation state description [Mo(3+)Fe(3+)Fe(2+)(2)]. Reaction of [(Tp)MoFe(3)S(4)(PEt(3))(2)Cl] with (Me(3)Si)(2)S affords [(Tp)MoFe(3)S(4)(PEt(3))(2)(SSiMe(3))], a likely first intermediate in the formation of the tricluster compound {[(Tp)MoFe(3)S(4)(PEt)(2)](3)S}(BPh(4)) from the reaction of [(Tp)MoFe(3)S(4)(PEt(3))(3)](BPh(4)) and NaSSiMe(3) in tetrahydrofuran (THF). The tricluster consists of three cluster units bound to a central μ(3)-S atom in a species of overall C(3) symmetry. Relatively few clusters in the [MoFe(3)S(4)](2+) oxidation state have been prepared compared to the abundance of clusters in the oxidized [MoFe(3)S(4)](3+) state. This work is the first comprehensive study of the [MoFe(3)S(4)](2+) state, one conspicuous feature of which is its ability to bind hard and soft σ-donors and strong to weak π-acid ligands. (Tp = tris(pyrazolyl)hydroborate(1-)).
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