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Published February 16, 1998 | public
Journal Article

A Cationic Imido Complex of Permethyltantalocene:  H_2 and Carbon−Hydrogen Bond Activation, [2 + 2] Cycloaddition Reactions, and an Unusual Reaction with Carbon Dioxide That Affords Coordinated Isocyanate


The cationic imido complex [Cp*2Ta(=NCMe_3)(THF)][B(C_6F_5)_4] (1) (Cp* = (η^5-C_5Me_5)) reacts with σ bonds H−X to afford [Cp*_2Ta(NHCMe_3)X][B(C_6F_5)_4] (X = Cl, OH, C⋮CR). Intramolecular activation of a carbon−hydrogen bond of a Cp* methyl group ultimately yields [Cp*Ta(η^5-C_5Me_4CH_2NCMe_3)H][B(C_6F_5)_4]. Reaction with carbon dioxide leads to dealkylation of the imido group, liberating isobutylene and yielding the isocyanate complex [Cp*_2Ta(OH)(NCO)][B(C_6F_5)_4].

Additional Information

© 1998 American Chemical Society. Received September 15, 1997. This work was supported by the National Science Foundation (Grant No. CHE-9506413), through a National Sciences and Energy Research Council of Canada (NSERC) postdoctoral fellowship to D.M.A., and through a National Science Foundation Predoctoral Fellowship to R.E.B.

Additional details

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