The first structurally characterized nitrosyl heme thiolate model complex

Abstract

The NO ligand in the formally {FeNO}6 compound [Fe(oep)(NO)(thiolate)] is bent, and does not impart a significant structural trans effect to the Fe-S bond.

Three Redox States of Metallonitrosyls in Aqueous Solution

“…The MNO angles range extends down to $150 , in parallel with decreasing values of υ NO that reach $1800 cm À1 . It is worth mentioning a heme-thiolate model that exhibits a FeNO angle of $160 (27) and ν NO at 1839 cm À1 , very close to values found for the NO-bound ferric P450nor containing trans-cysteine (54). Similar results were reported for a model of the inactive form of NH ase with a trans-SR À ligand to nitrosyl (28).…”

Studies of Iron(III) Porphyrinates Containing Silanethiolate Ligands

“…We favor the former based on similar findings by Richter-Addo. 61 The final gaseous small molecule examined was H 2 S. Treatment of [Fe(STIPS)(TMP)] with 1 atm of H 2 S in benzene- d 6 lead to immediate reduction and formation of [Fe II (TMP)] in similar fashion to reactions starting from [Fe(OH)(H 2 O)(TMP)].…”

Nitrosylation in a Crystal: Remarkable Movements of Iron Porphyrins Upon Binding of Nitric Oxide

“…We previously reported the preparation of a heme nitrosyl thiolate compound using a unique solid-gas reaction that allowed X-ray structural characterization. [9] Herein, we report that we have utilized gaseous diffusion of NO into a suitably constructed crystal of the five-coordinate precursor [(TPP)Fe(H 2 O)]SO 3 CF 3 (1) to generate the nitrosyl derivative as determined by IR spectroscopy and singlecrystal X-ray crystallography. This solid-gas reaction permits, for the first time, a detailed structural comparison between the precursor compound and its NO adduct in the same crystal under identical experimental conditions.…”