Blake, Robert E., Jr. and Antonelli, David M. and Henling, Lawrence M. and Schaefer, William P. and Hardcastle, Kenneth I. and Bercaw, John E. (1998) 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. Organometallics, 17 (4). pp. 718-725. ISSN 0276-7333. http://resolver.caltech.edu/CaltechAUTHORS:20180518-161116349
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Abstract
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].
| Item Type: | Article | ||||||||
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| Alternate Title: | A Cationic Imido Complex of Permethyltantalocene: H2 and Carbon−Hydrogen Bond Activation, [2 + 2] Cycloaddition Reactions, and an Unusual Reaction with Carbon Dioxide That Affords Coordinated Isocyanate | ||||||||
| 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. | ||||||||
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| Record Number: | CaltechAUTHORS:20180518-161116349 | ||||||||
| Persistent URL: | http://resolver.caltech.edu/CaltechAUTHORS:20180518-161116349 | ||||||||
| Official Citation: | A Cationic Imido Complex of Permethyltantalocene: H2 and Carbon−Hydrogen Bond Activation, [2 + 2] Cycloaddition Reactions, and an Unusual Reaction with Carbon Dioxide That Affords Coordinated Isocyanate Robert E. Blake, Jr., David M. Antonelli, Larry M. Henling, William P. Schaefer, Kenneth I. Hardcastle, and John E. Bercaw Organometallics 1998 17 (4), 718-725 DOI: 10.1021/om970815p | ||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||
| ID Code: | 86478 | ||||||||
| Collection: | CaltechAUTHORS | ||||||||
| Deposited By: | George Porter | ||||||||
| Deposited On: | 21 May 2018 15:59 | ||||||||
| Last Modified: | 21 May 2018 15:59 |
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