Formation of a Sulfur-Atom-Inserted N-Confused Porphyrin Iron Nitrosyl Complex by Denitrosation and C<i>−</i>S Bond Cleavage of an <i>S-</i>Nitrosothiol

Abstract

The reaction of nitrosothiol, Ph3CSNO, with a divalent iron N-confused porphyrin complex, Fe(HCTPPH)Br, yields a {Fe(NO)}6 iron nitrosyl complex with a sulfur atom inserted in the Fe-C bond. The crystal structure reveals a bent Fe-N-O geometry and an eta2-(C,S) bonding mode between iron and the C-S bond. A reaction mechanism involving a transnitrosation and a nitrosothiol C-S bond cleavage is proposed.