Smith, David C. and Gray, Harry B. (1989) Atom-Transfer Reactivity of Binuclear d^8 Complexes. In: The Challenge of d and f Electrons. ACS Symposium Series. No.394. American Chemical Society , Washington, DC, pp. 356-365. ISBN 9780841216280. https://resolver.caltech.edu/CaltechAUTHORS:20180405-103147632
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Abstract
The long-lived ^3(dσ^*pσ) state of binuclear d8 complexes undergoes a variety of reactions. One prominent reaction, photooxidative addition of halocarbons, apparently proceeds by halogen atom transfer rather than outersphere electron transfer. Excited-state hydrogen atom transfer occurs in reactions between several binuclear d^8 complexes and a number of organic and organometallic substrates. Specific results for Pt_2(P_2O_5H_2)_4^(4-) and Ir_2(TMB)_4^(2+) (TMB = 2,5-diisocyano-2,5-dimethylhexane) are discussed. Production of a hole in the dσ* orbital is believed to be an important factor in these photochemical atom-transfer reactions. Electrochemical generation of such a hole produces a highly reactive intermediate that can undergo atom abstraction, thereby yielding net oxidation of an organic substrate. The net reaction is electrocatalytic in metal complex.
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| Additional Information: | © 1989 American Chemical Society. Received March 8, 1989. Published in print 8 June 1989. Our research on binuclear complexes has been supported by the Sun Company and by National Science Foundation Grant CHE84-19828. This is contribution no. 7897 from the Arthur Amos Noyes Laboratory. | |||||||||
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| Series Name: | ACS Symposium Series | |||||||||
| Issue or Number: | 394 | |||||||||
| DOI: | 10.1021/bk-1989-0394.ch025 | |||||||||
| Record Number: | CaltechAUTHORS:20180405-103147632 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180405-103147632 | |||||||||
| Official Citation: | Atom-Transfer Reactivity of Binuclear d8 Complexes David C. Smith and Harry B. Gray The Challenge of d and f Electrons. June 8, 1989 , 356-365 DOI:10.1021/bk-1989-0394.ch025 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 85633 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 05 Apr 2018 20:58 | |||||||||
| Last Modified: | 15 Nov 2021 20:30 |
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