Dinitrosyl iron complexes relevant to Rieske cluster nitrosylation.

Reaction of the Rieske cluster model complex (Et(4)N)(2)[(N(2)CHPh)Fe(2)S(2)(S(2)-o-xyl)] (N(2)CHPh = dianion of 2,2'-(phenylmethylene)bis(3-methylindole); S(2)-o-xyl = dianion of 1,2-phenylenedimethanethiol) with nitric oxide results in disassembly of the iron-sulfur core and formation of {Fe(NO)(2)}(9) dinitrosyliron complexes (DNICs). Isolation and characterization of these DNICs, including the new compound, (Et(4)N)[(N(2)CHPh)Fe(NO)(2)], demonstrates a homology between the synthetic Riekse cluster and purely thiolate-bound Fe(2)S(2) clusters in reactions involving NO. To model the nitrogen-rich environment of Rieske cluster-derived dinitroysliron species, a new type of neutral {Fe(NO)(2)}(9) DNIC was prepared containing a beta-diketiminate ligand. One-electron reduction of this compound affords the isolable {Fe(NO)(2)}(10) DNIC. These compounds represent a rare example of structurally analogous DNIC redox partners.