Hydride Attack on a Coordinated Ferric Nitrosyl: Experimental and DFT Evidence for the Formation of a Heme Model–HNO Derivative
Erwin G. Abucayon†, Rahul L. Khade‡, Douglas R. Powell†, Yong Zhang*‡, and George B. Richter-Addo*†
† Department
of Chemistry and Biochemistry, University
of Oklahoma, Norman, Oklahoma 73019, United
States
‡ Department
of Biomedical Engineering, Chemistry and Biological Sciences, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, New Jersey 07030, United States
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/jacs.5b12008
Publication Date (Web): December 17, 2015
Copyright © 2015 American Chemical Society
*yong.zhang@stevens.edu (DFT), *grichteraddo@ou.edu (experimental)
Abstract
Heme–HNO
species are crucial intermediates in several biological processes. To
date, no well-defined Fe heme–HNO model compounds have been reported.
Hydride attack on the cationic ferric [(OEP)Fe(NO)(5-MeIm)]OTf (OEP =
octaethylporphyrinato dianion) generates an Fe–HNO product that has been
characterized by IR and 1H NMR spectroscopy. Results of DFT
calculations reveal a direct attack of the hydride on the N atom of the
coordinated ferric nitrosyl.
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