The discovery of intermediate Q  by Lipscomb and M�nck in the catalytic cycle of soluble methane monooxygenase (sMMO-Q  ) two decades ago was a landmark development, marking the first time that a high-valent iron species could be spectroscopically identified during the turnover of a dioxygen activating nonheme iron enzyme.1 This groundbreaking study showed that intermediate Q  must have an antiferromagnetically coupled diiron(IV) center and initiated EXAFS experiments that led to the proposal of an FeIV2(�-O)2 diamond core for sMMO-Q  .2 Efforts in my lab focused on obtaining synthetic analogues of sMMO-Q  have led to the only crystal structures of high-valent complexes with Fe2(�-O)2 diamond cores, including that recently obtained for a complex with an FeIV2(�-O)2 core.3 These results provide insight into the metric parameters that define the FeIV2(�-O)2 core. In addition, we have investigated the chemistry required for diamond core formation and the factors affecting their C�H bond cleavage reactivity.4These aspects will be discussed.Lee, S.-K.; Fox, B. G.; Froland, W. A.; Lipscomb, J. D.; M�nck, E., A Transient Intermediate of the Methane Monooxygenase Catalytic Cycle Containing an FeIVFeIV Cluster J. Am. Chem. Soc. 1993  , 115, 6450.Shu, L.; Nesheim, J. C.; Kauffmann, K.; M�nck, E.; Lipscomb, J. D.; Que, L., Jr., An Fe2IVO2 Diamond Core Structure for the Key Intermediate Q of Methane Monooxygenase Science 1997  , 275, 515.Xue, G.; Wang, D.; De Hont, R.; Fiedler, A. T.; Shan, X.; M�nck, E.; Que, L., Jr., A Synthetic Precedent for the [FeIV2(�-O)2] Diamond Core Proposed for Methane Monooxygenase Intermediate Q Proc. Nat. Acad. Sci. USA 2007  , 104, 20713.Xue, G.; De Hont, R.; M�nck, E.; Que, L., Jr., Million-fold activation of the [Fe2(�-O)2] diamond core for C�H bond cleavage Nature Chem. 2010  , 2, 400.

Biomimetic studies inspired by the work of John Lipscomb

248th National Meeting (2014)

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