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Femtosecond Dynamics and Electrocatalysis of the Reduction of O_2: Tetraruthenated Cobalt Porphyrins

Yu, Hua-Zhong and Baskin, J. Spencer and Steiger, Beat and Anson, Fred C. and Zewail, Ahmed H. (1999) Femtosecond Dynamics and Electrocatalysis of the Reduction of O_2: Tetraruthenated Cobalt Porphyrins. Journal of the American Chemical Society, 121 (2). pp. 484-485. ISSN 0002-7863. doi:10.1021/ja983532c.

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Recently we reported the femtosecond dynamics of some porphyrin molecules. These studies elucidated the elementary steps involved in intramolecular relaxation and charge transfer (CT) in cobalt tetraphenylporphyrin (CoTPP) from the porphyrin π (a_(2u)) system to the Co(d_z^2). Our interest in the dynamics of intramolecular electron transfer stems from recent studies of cobalt porphyrins that were modified by attachment of Ru(II) or Os(II) complexes to the periphery of the porphyrin ring. These modified cobalt porphyrins exhibit high catalytic activity for the electroreduction of O_2 directly to H_2O, a process that most monomeric cobalt porphyrins are unable to accomplish. The mechanism by which the modified cobalt porphyrins achieve the direct, four-electron reduction of O_2 has been suggested to involve back-bonding interactions among the attached Ru(II) and Os(II) centers, the porphyrin ring, and the Co(II) ion at its center.

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Additional Information:© 1999 American Chemical Society. Received October 6, 1998. Publication Date (Web): December 31, 1998. This work was supported by the National Science Foundation (Laboratory for Molecular Sciences). We wish to thank Mr. Björn Önfelt for his assistance with some of the experiments.
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Official Citation:Femtosecond Dynamics and Electrocatalysis of the Reduction of O2:  Tetraruthenated Cobalt Porphyrins Hua-Zhong Yu, J. Spencer Baskin, Beat Steiger, Fred C. Anson, and Ahmed H. Zewail Journal of the American Chemical Society 1999 121 (2), 484-485 DOI: 10.1021/ja983532c
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:69855
Deposited By: Ruth Sustaita
Deposited On:26 Aug 2016 18:15
Last Modified:11 Nov 2021 04:20

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