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Atom-Transfer Reactivity of Binuclear d^8 Complexes

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.

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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.

Item Type:Book Section
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Gray, Harry B.0000-0002-7937-7876
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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Arthur Amos Noyes Laboratory of Chemical Physics7897
Series Name:ACS Symposium Series
Issue or Number:394
Record Number:CaltechAUTHORS:20180405-103147632
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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
Deposited By: Ruth Sustaita
Deposited On:05 Apr 2018 20:58
Last Modified:15 Nov 2021 20:30

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