Hydride Attack on a Coordinated Ferric Nitrosyl: Experimental and DFT Evidence for the Formation of a Heme Model–HNO Derivative

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.