Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published June 8, 1989 | public
Book Section - Chapter

Atom-Transfer Reactivity of Binuclear d^8 Complexes

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

Created:
August 19, 2023
Modified:
January 14, 2024