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|Title:||A nanosecond laser flash photolysis study of remote intramolecular phenolic hydrogen atom abstraction by carbonyl triplets|
|Authors:||St. Pierre, Michael|
|Abstract:||<p> It has been shown that the hydroxy compounds la-4a possess triplet states which are substantially shorter-lived than those of their methoxy analogs (lb-4b). In each case the efficient quenching of the excited carbonyl triplet state has been attributed to intramolecular phenolic hydrogen abstraction. Evidence for this is found in the detection of biradical species generated from triplet decay, primary hydrogen-deuterium kinetic isotope effects and thermodynamic parameters which support both atom transfer (enthalpy) and high degrees of order (entropy) in the transition state necessary for the proposed abstraction process. The difference in triplet lifetimes (16 ns to 1135 ns) is due almost exclusively to varying degrees of difficulty in obtaining a transition state geometry in which the phenoxy hydrogen is properly lined up for intramolecular hydrogen abstraction. </p>|
|Appears in Collections:||Open Access Dissertations and Theses|
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|St.Pierre_Micheal_J_1995_Masters.pdf||13.54 MB||Adobe PDF||View/Open|
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