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Updated: Jun 20, 2026
Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Cubane-type Co4S4 clusters: synthesis, redox series, and magnetic ground states
Liang Deng1, Eckhard Bill, Karl Wieghardt
1Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
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 effective electron donor to tetrahedral Fe(II) and Co(II) sites. Clusters 3-6 have the same overall cubane-type geometry as 9. Neutral clusters 3 and 5 have an S = 3 ground state. As with the S = 4 state of 9 with local spins S(Fe) = 2, the septet spin state can be described in terms of the coupling of three parallel and one antiparallel spins S(Co) = 3/2. The octanuclear clusters [Co(8)S(8)(PPr(i)(3))(6)](0,1+) were isolated as minor byproducts of the formation and chemical oxidation of 3. The clusters exhibit a rhomb-bridged noncubane (RBNC) structure, whereas clusters with the Fe(8)S(8) core possess edge-bridged double-cubane (EBDC) stereochemistry. There are two structural solutions for the M(8)S(8) core in the form of topological isomers whose stability may depend on valence electron count. A conceptual model for the RBNC <--> EBDC interconversion is presented. (Pr(i)(2)NHCMe(2) = C(11)H(20)N(2) = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene).
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