title: Synthesis and electronic structure of cationic, neutral, and anionic bis(imino)pyridine iron alkyl complexes: evaluation of redox activity in single-component ethylene polymerization catalysts.
abstract: A family of cationic, neutral, and anionic bis(imino)pyridine iron alkyl complexes has been prepared, and their electronic and molecular structures have been established by a combination of X-ray diffraction, Mössbauer spectroscopy, magnetochemistry, and open-shell density functional theory. For the cationic complexes, [((iPr)PDI)Fe-R][BPh(4)] ((iPr)PDI = 2,6-(2,6-(i)Pr(2)-C(6)H(3)N═CMe)(2)C(5)H(3)N; R = CH(2)SiMe(3), CH(2)CMe(3), or CH(3)), which are known single-component ethylene polymerization catalysts, the data establish high spin ferrous compounds (S(Fe) = 2) with neutral, redox-innocent bis(imino)pyridine chelates. One-electron reduction to the corresponding neutral alkyls, ((iPr)PDI)Fe(CH(2)SiMe(3)) or ((iPr)PDI)Fe(CH(2)CMe(3)), is chelate-based, resulting in a bis(imino)pyridine radical anion (S(PDI) = 1/2) antiferromagnetically coupled to a high spin ferrous ion (S(Fe) = 2). The neutral neopentyl derivative was reduced by an additional electron and furnished the corresponding anion, [Li(Et(2)O)(3)][((iPr)PDI)Fe(CH(2)CMe(3))N(2)], with concomitant coordination of dinitrogen. The experimental and computational data establish that this S = 0 compound is best described as a low spin ferrous compound (S(Fe) = 0) with a closed-shell singlet bis(imino)pyridine dianion (S(PDI) = 0), demonstrating that the reduction is ligand-based. The change in field strength of the bis(imino)pyridine coupled with the placement of the alkyl ligand into the apical position of the molecule induced a spin state change at the iron center from high to low spin. The relevance of the compounds and their electronic structures to olefin polymerization catalysis is also presented.
authors.affiliation: Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, USA.
authors.forename: Aaron M
authors.initials: AM
authors.lastname: Tondreau
authors.forename: Carsten
authors.initials: C
authors.lastname: Milsmann
authors.forename: Andrew D
authors.initials: AD
authors.lastname: Patrick
authors.forename: Helen M
authors.initials: HM
authors.lastname: Hoyt
authors.forename: Emil
authors.initials: E
authors.lastname: Lobkovsky
authors.forename: Karl
authors.initials: K
authors.lastname: Wieghardt
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Chirik
mesh_terms: D000838:Anions; D002412:Cations; D005030:Ethylenes / Q000737:chemistry*; D058085:Iron Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D011108:Polymers / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*
chemical_list: D000838:Anions; D002412:Cations; D005030:Ethylenes; D058085:Iron Compounds; D011108:Polymers; D011725:Pyridines; C036216:ethylene