Formation of a sulfur-atom-inserted n-confused porphyrin iron nitrosyl complex by denitrosation and C-S bond cleavage of an S-nitrosothiol

The reaction of nitrosothiol, Ph3CSNO, with a divalent iron N-confused porphyrin complex, Fe(HCTPPH)Br, yields a {Fe(NO)}(16) 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 eta(2)-(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.