title: Unusual iron(III) ate complexes stabilized by Li-pi interactions.
abstract: Several iron(III) complexes incorporating diamidoether ligands are described. The reaction between [Li(2)[RN(SiMe(2))](2)O] and FeX(3) (X=Cl or Br; R=2,4,6-Me(3)Ph or 2,6-iPr(2)Ph) form unusual ate complexes, [FeX(2)Li[RN(SiMe(2))](2)O](2) (2, X=Cl, R=2,4,6-Me(3)Ph; 3, X=Br, R=2,4,6-Me(3)Ph; 4, X=Cl, R=2,6-iPr(2)Ph) which are stabilized by Li-pi interactions. These dimeric iron(III)-diamido complexes exhibit magnetic behaviour characteristic of uncoupled high spin (S= 5/2 ) iron(III) centres. They also undergo halide metathesis resulting in reduced iron(II) species. Thus, reaction of 2 with alkyllithium reagents leads to the formation of iron(II) dimer [Fe[Me(3)PhN(SiMe(2))](2)O](2) (6). Similarly, the previously reported iron(III)-diamido complex [FeCl[tBuN(SiMe(2))](2)O](2) (1) reacts with LiPPh(2) to yield the iron(II) dimer [Fe[tBuN(SiMe(2))](2)O](2) but reaction with LiNPh(2) gives the iron(II) product [Fe(2)(NPh(2))(2)[tBuN(SiMe(2))](2)O] (5). Some redox chemistry is also observed as side reactions in the syntheses of 2-4, yielding THF adducts of FeX(2): the one-dimensional chain [FeBr(2)(THF)(2)](n) (7) and the cluster [Fe(4)Cl(8)(THF)(6)]. The X-ray crystal structures of 3, 5 and 7 are described.
authors.affiliation: Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, BC V5A 1S6, Canada.
authors.forename: Garry
authors.initials: G
authors.lastname: Mund
authors.forename: Dragoslav
authors.initials: D
authors.lastname: Vidovic
authors.forename: Raymond J
authors.initials: RJ
authors.lastname: Batchelor
authors.forename: James F
authors.initials: JF
authors.lastname: Britten
authors.forename: Rajendra D
authors.initials: RD
authors.lastname: Sharma
authors.forename: Colin H W
authors.initials: CH
authors.lastname: Jones
authors.forename: Daniel B
authors.initials: DB
authors.lastname: Leznoff