Reactions of group III biheterocyclic complexes.
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.
Carver
Colin T
CT
Department of Chemistry & Biochemistry, University of California, Los Angeles, California 90095, USA.
Benitez
Diego
D
Miller
Kevin L
KL
Williams
Bryan N
BN
Tkatchouk
Ekaterina
E
Goddard
William A
WA
Diaconescu
Paula L
PL
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
D006571:Heterocyclic Compounds; D008024:Ligands; D008674:Metals, Rare Earth; D009942:Organometallic Compounds