A Synthetic Model of the Putative Fe(II)-Iminobenzosemiquinonate Intermediate in the Catalytic Cycle of o-Aminophenol Dioxygenases

Authors

Michael M. Bittner, Marquette UniversityFollow
Sergey V. Lindeman, Marquette UniversityFollow
Adam T. Fiedler, Marquette UniversityFollow

Document Type

Article

Language

eng

Format of Original

4 p.

Publication Date

2012

Publisher

American Chemical Society

Source Publication

Journal of the American Chemical Society

Source ISSN

0002-7863

Original Item ID

DOI: 10.1021/ja212163t

Abstract

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)(ISQ^tBu) (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.

Comments

Accepted version. Journal of the American Chemical Society, Vol. 134, No. 12 (2012): 5460-5463. DOI. © 2012 American Chemical Society. Used with permission.

Recommended Citation

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.
https://epublications.marquette.edu/chem_fac/386