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.

DOI: 10.1021/ja902794w

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Cite this paper

@article{Carver2009ReactionsOG, title={Reactions of group III biheterocyclic complexes.}, author={Colin T Carver and Diego Ben{\'i}tez and Kevin L Miller and Bryan N Williams and Ekaterina Tkatchouk and William A. Goddard and Paula L Diaconescu}, journal={Journal of the American Chemical Society}, year={2009}, volume={131 29}, pages={10269-78} }