Atom-Transfer Reactivity of Binuclear d^8 Complexes
- Creators
- Smith, David C.
- Gray, Harry B.
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.
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.Additional details
- Eprint ID
- 85633
- Resolver ID
- CaltechAUTHORS:20180405-103147632
- CHE84-19828
- NSF
- Created
-
2018-04-05Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field
- Series Name
- ACS Symposium Series
- Series Volume or Issue Number
- 394
- Other Numbering System Name
- Arthur Amos Noyes Laboratory of Chemical Physics
- Other Numbering System Identifier
- 7897