C−H Bond Activation of Benzene by Unsaturated η2-Cyclopropene and η2-Benzyne 
Complexes of Niobium

Boulho, Cédric; Oulié, Pascal; Vendier, Laure; Etienne, Michel; Pimienta, Véronique; Locati, Abel; Bessac, Fabienne; Maseras, Feliu; Pantazis, Dimitrios A.; McGrady, John E.

doi:10.1021/ja1061505

Item

ITEM ACTIONSEXPORT

Add to Basket

Local TagsRelease HistoryDetailsSummary

Released

Journal Article

C−H Bond Activation of Benzene by Unsaturated η2-Cyclopropene and η2-Benzyne Complexes of Niobium

MPS-Authors

There are no MPG-Authors in the publication available

External Resource

No external resources are shared

Fulltext (restricted access)

There are currently no full texts shared for your IP range.

Fulltext (public)

There are no public fulltexts stored in PuRe

Supplementary Material (public)

There is no public supplementary material available

Citation

Boulho, C., Oulié, P., Vendier, L., Etienne, M., Pimienta, V., Locati, A., et al. (2010). C−H Bond Activation of Benzene by Unsaturated η2-Cyclopropene and η2-Benzyne Complexes of Niobium. Journal of the American Chemical Society, 132(40), 14239-14250. doi:10.1021/ja1061505.

Cite as: https://hdl.handle.net/21.11116/0000-0007-3637-F

Abstract

We report the synthesis of a niobium cyclopropyl complex, Tp^Me2NbMe(c-C₃H₅)(MeCCMe), and show that thermal loss of methane from this compound generates an intermediate that is capable of activating both aliphatic and aromatic C−H bonds. Isotopic labeling, trapping studies, a detailed kinetic analysis, and density functional theory all suggest that the active intermediate is an η²-cyclopropene complex formed via β-hydrogen abstraction rather than an isomeric cyclopropylidene species. C−H activation chemistry of this type represents a rather unusual reactivity pattern for η²-alkene complexes but is favored in this case by the strain in the C₃ ring which prevents the decomposition of the key intermediate via loss of cyclopropene.