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• W2322306746 startingPage "6280" @default.
• W2322306746 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-))." @default.
• W2322306746 created "2016-06-24" @default.
• W2322306746 creator A5046148479 @default.
• W2322306746 creator A5052881048 @default.
• W2322306746 date "2011-06-07" @default.
• W2322306746 modified "2023-10-17" @default.
• W2322306746 title "The [MoFe₃S₄]²⁺ Oxidation State: Synthesis, Substitution Reactions, and Structures of Phosphine-Ligated Cubane-Type Clusters with the <i>S</i> = 2 Ground State" @default.
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• W2322306746 doi "https://doi.org/10.1021/ic200641k" @default.
• W2322306746 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/3160175" @default.
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• W2322306746 hasPublicationYear "2011" @default.
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