A Synthetic Model of the Putative Fe(II)-Iminobenzosemiquinonate Intermediate in the Catalytic Cycle of o-Aminophenol Dioxygenases
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American Chemical Society
Journal of the American Chemical Society
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The oxidative ring cleavage of aromatic substrates by nonheme Fe dioxygenases is thought to involve formation of a ferrous–(substrate radical) intermediate. Here we describe the synthesis of the trigonal-bipyramdial complex Fe(Ph2Tp)(ISQtBu) (2), the first synthetic example of an iron(II) center bound to an iminobenzosemiquinonate (ISQ) radical. The unique electronic structure of this S = 3/2 complex and its one-electron oxidized derivative (+) have been established on the basis of crystallographic, spectroscopic, and computational analyses. These findings further demonstrate the viability of Fe2+–ISQ intermediates in the catalytic cycles of o-aminophenol dioxygenases.
Bittner, Michael M.; Lindeman, Sergey V.; and Fiedler, Adam T., "A Synthetic Model of the Putative Fe(II)-Iminobenzosemiquinonate Intermediate in the Catalytic Cycle of o-Aminophenol Dioxygenases" (2012). Chemistry Faculty Research and Publications. 386.
Accepted version. Journal of the American Chemical Society, Vol. 134, No. 12 (2012): 5460-5463. DOI. © 2012 American Chemical Society. Used with permission.