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Femtosecond Dynamics of Dioxygen - Picket-Fence Cobalt Porphyrins: Ultrafast Release of O_2 and the Nature of Dative Bonding

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.

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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.

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URLURL TypeDescription<257::AID-ANIE257>3.0.CO;2-3DOIArticle;2-3/abstractPublisherArticle
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
Record Number:CaltechAUTHORS:20160819-142157037
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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
Deposited By: Ruth Sustaita
Deposited On:22 Aug 2016 22:47
Last Modified:11 Nov 2021 04:19

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