Cubane-type Co4S4 clusters: synthesis, redox series, and magnetic ground states.

ABSTRACT: The recent demonstration that the carbene cluster [Fe(4)S(4)(Pr(i)(2)NHCMe(2))(4)] (9) is an accurate structural and electronic analogue of the fully reduced cluster of the iron protein of Azotobacter vinelandii nitrogenase, including a common S = 4 ground state, raises the issue of the existence and magnetism of other [M(4)S(4)L(4)](z) clusters, none of which are known with transition metals other than iron. The system CoCl(2)/Pr(i)(3)P/(Me(3)Si)(2)S/THF assembles [Co(4)S(4)(PPr(i)(3))(4)] (3), which is converted to [Co(4)S(4)(Pr(i)(2)NHCMe(2))(4)] (5) upon reaction with carbene. The clusters support the redox series [3](1-/0/1+) and [5](0/1+/2+); monocations (4, 6) have been isolated by chemical oxidation. Redox potentials and substitution reactions indicate that the carbene is the more

SUBMITTER: Deng L 

PROVIDER: S-EPMC3170832 | biostudies-literature | 2009 Aug

REPOSITORIES: biostudies-literature