The [MoFe3S4]2+ oxidation state: synthesis, substitution reactions, and structures of phosphine-ligated cubane-type clusters with the S=2 ground state.

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)Mo

SUBMITTER: Xi B 

PROVIDER: S-EPMC3160175 | biostudies-literature | 2011 Jul

REPOSITORIES: biostudies-literature