Steiger, Beat and Baskin, J. Spencer and Anson, Fred C. and Zewail, Ahmed H. (2000) Femtosecond Dynamics of Dioxygen - Picket-Fence Cobalt Porphyrins: Ultrafast Release of O_2 and the Nature of Dative Bonding. Angewandte Chemie International Edition, 39 (1). pp. 257-260. ISSN 1433-7851. doi:10.1002/(SICI)1521-3773(20000103)39:1<257::AID-ANIE257>3.0.CO;2-3. https://resolver.caltech.edu/CaltechAUTHORS:20160819-142157037
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Abstract
The ultrafast release of O_2 from the O_2 adduct of picket-fence cobalt porphyrin (see picture) has been probed in real time, and has a total reaction time of 2 ps, without subsequent recombination over several nanoseconds. The dynamics of this ultrafast release of O_2 shows that relaxation within the porphyrin system (200 fs) precedes porphyrin-to-metal electron transfer, but the latter occurs at an enhanced rate (500 fs as opposed to the more usual 1 – 2 ps) because of the dative bonding of cobalt and O_2, which gives the adduct ground state significant Co^(III)−O_2^− character.
| Item Type: | Article | ||||
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| Additional Information: | © 2000 Wiley-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany. Received: September 23, 1999. Version of Record online: 12 Jan 2000. This work was supported by the US National Science Foundation (Laboratory for Molecular Sciences). | ||||
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| Subject Keywords: | cobalt; femtochemistry; laser spectroscopy; O−O activation; porphyrinoids | ||||
| Issue or Number: | 1 | ||||
| DOI: | 10.1002/(SICI)1521-3773(20000103)39:1<257::AID-ANIE257>3.0.CO;2-3 | ||||
| Record Number: | CaltechAUTHORS:20160819-142157037 | ||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20160819-142157037 | ||||
| Official Citation: | Steiger, B., Baskin, J. S., Anson, F. C. and Zewail, A. H. (2000), Femtosecond Dynamics of Dioxygen – Picket-Fence Cobalt Porphyrins: Ultrafast Release of O2 and the Nature of Dative Bonding. Angew. Chem. Int. Ed., 39: 257–260. doi: 10.1002/(SICI)1521-3773(20000103)39:1<257::AID-ANIE257>3.0.CO;2-3 | ||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||
| ID Code: | 69800 | ||||
| Collection: | CaltechAUTHORS | ||||
| Deposited By: | Ruth Sustaita | ||||
| Deposited On: | 22 Aug 2016 22:47 | ||||
| Last Modified: | 11 Nov 2021 04:19 |
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