A Synthetic Model of the Putative Fe(II)-Iminobenzosemiquinonate Intermediate in the Catalytic Cycle of \u3cem\u3eo\u3c/em\u3e-Aminophenol Dioxygenases

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 [sic] 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 ([3]+) 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