A Terminal Imido Complex of an Iron-Sulfur Cluster.

2021 
We report the synthesis and characterization of the first terminal imido complex of an Fe-S cluster, (IMes)3Fe4S4=NDipp (2; IMes = 1,3-dimesitylimidazol-2-ylidene, Dipp = 2,6-diisopropylphen-yl), which is generated by oxidative group transfer from DippN3 to the all-ferrous cluster (IMes)3Fe4S4(PPh3). This two-electron process is achieved by formal one-electron oxidation of the imido-bound Fe site and one-electron oxidation of two IMes-bound Fe sites. Structural, spectroscopic, and computational studies establish that the Fe-imido site is best described as a high-spin Fe3+ center, which is reflected in its long Fe-N(imido) distance of 1.763(2) A. Cluster 2 abstracts hydrogen atoms from 1,4-cyclohexadiene to yield the corresponding anilido complex, demonstrating competency for C-H activation.
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