title: Dinitrosyl iron complexes relevant to Rieske cluster nitrosylation.
abstract: 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.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Zachary J
authors.initials: ZJ
authors.lastname: Tonzetich
authors.forename: Loi H
authors.initials: LH
authors.lastname: Do
authors.forename: Stephen J
authors.initials: SJ
authors.lastname: Lippard
mesh_terms: D014450:Electron Transport Complex III / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D009589:Nitrogen Oxides / Q000737:chemistry*
chemical_list: D009589:Nitrogen Oxides; C037989:Rieske iron-sulfur protein; C073661:dinitrosyl iron complex; D007501:Iron; D014450:Electron Transport Complex III