An unusual zwitterionic, diradical intermediate in photochemical electron-transfer substitution reactions.
John B Miller, Jeremy Breeding, Thomas J Smith
Index: J. Am. Chem. Soc. 126(40) , 12742-3, (2004)
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Abstract
An unusual zwitterionic diradical intermediate complex R*...X-...HR'B*+ is generated during the photoinduced electron-transfer substitution reaction between alkyl halides (RX) and Lewis bases (HR'B). This reaction intermediate was observed for the 1-chloroadamantane and tert-butylamine system in a hydrocarbon glass at 25 K by electron spin resonance spectroscopy. Ab initio density functional calculations were carried out to examine the physical and electronic structure of the intermediate.
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