title: Reactions of group III biheterocyclic complexes.
abstract: Group III alkyl complexes supported by a ferrocene diamide ligand (1,1'-fc(NSi(t)BuMe(2))(2)) have been found to be reactive toward aromatic N-heterocycles such as 1-methylimidazole and pyridines. These reactions were investigated experimentally and computationally. An initial C-H activation event is followed by a coupling reaction to form biheterocyclic complexes, in which one of the rings is dearomatized. In the case of 1-methylimidazole, the biheterocyclic compound could not be isolated and further led to an imidazole ring-opened product; in the case of pyridines, it transformed into an isomer with extended conjugation of double bonds. Mechanisms for both reactions are proposed on the basis of experimental and computational results. DFT calculations were also used to show that an energetically accessible pathway for the ring-opening of pyridines exists.
authors: Department of Chemistry & Biochemistry, University of California, Los Angeles, California 90095, USA.
authors: Colin T
authors: CT
authors: Carver
authors: Diego
authors: D
authors: Benitez
authors: Kevin L
authors: KL
authors: Miller
authors: Bryan N
authors: BN
authors: Williams
authors: Ekaterina
authors: E
authors: Tkatchouk
authors: William A
authors: WA
authors: Goddard
authors: Paula L
authors: PL
authors: Diaconescu
mesh_terms: D003198:Computer Simulation; D018360:Crystallography, X-Ray; D006571:Heterocyclic Compounds / Q000737:chemistry*; D008024:Ligands; D008674:Metals, Rare Earth / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D006571:Heterocyclic Compounds; D008024:Ligands; D008674:Metals, Rare Earth; D009942:Organometallic Compounds