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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

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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https://dx.doi.org/10.1021/om970815pDOIArticle
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.
Funders:
Funding AgencyGrant Number
NSFCHE-9506413
Natural Sciences and Engineering Research Council of Canada (NSERC)UNSPECIFIED
NSF Predoctoral FellowshipUNSPECIFIED
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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