title: Reactivity and Mössbauer spectroscopic characterization of an Fe(IV) ketimide complex and reinvestigation of an Fe(IV) norbornyl complex.
abstract: Thermolysis of Fe(N═C(t)Bu2)4 (1) for 8 h at 50 °C generates the mixed valent Fe(III)/Fe(II) bimetallic complex Fe2(N═C(t)Bu2)5 (2) in moderate yield. Also formed in this reaction are tert-butyl cyanide, isobutane, and isobutylene, the products of ketimide oxidation by the Fe(4+) center. Reaction of 1 with 1 equiv of acetylacetone affords the Fe(III) complex, Fe(N═C(t)Bu2)2(acac) (3), concomitant with formation of bis(tert-butyl)ketimine, tert-butyl cyanide, isobutane, and isobutylene. In addition, the Mössbauer spectra of 1 and its lower-valent analogues [Li(12-crown-4)2][Fe(N═C(t)Bu2)4] (5) and [Li(THF)]2[Fe(N═C(t)Bu2)4] (6) were recorded. We also revisited the chemistry of Fe(1-norbornyl)4 (4) to elucidate its solid-state molecular structure and determine its Mössbauer spectrum, for comparison with that recorded for 1.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.
authors.forename: Richard A
authors.initials: RA
authors.lastname: Lewis
authors.forename: Danil E
authors.initials: DE
authors.lastname: Smiles
authors.forename: Jonathan M
authors.initials: JM
authors.lastname: Darmon
authors.forename: S Chantal E
authors.initials: SC
authors.lastname: Stieber
authors.forename: Guang
authors.initials: G
authors.lastname: Wu
authors.forename: Trevor W
authors.initials: TW
authors.lastname: Hayton
mesh_terms: D000475:Alkenes / Q000737:chemistry; D003486:Cyanides / Q000737:chemistry; D007097:Imines / Q000737:chemistry; D058085:Iron Compounds / Q000737:chemistry*; D008958:Models, Molecular; D009570:Nitriles / Q000737:chemistry; D009636:Norbornanes / Q000737:chemistry*; D015204:Spectroscopy, Mossbauer
chemical_list: D000475:Alkenes; D003486:Cyanides; D007097:Imines; D058085:Iron Compounds; D009570:Nitriles; D009636:Norbornanes; C542835:ketimine; C008176:isobutylene