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Theoretical Study on the Origin of the Behavior of Ketones and Thiones in Hydrogen Photoabstraction Reactions
Author(s) -
Bigot B.
Publication year - 1983
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.198300016
Subject(s) - chemistry , excited state , hydrogen , hydrogen atom , ab initio , ketone , acceptor , carbon fibers , transition state , computational chemistry , atom (system on chip) , carbon atom , photochemistry , atomic physics , catalysis , organic chemistry , group (periodic table) , ring (chemistry) , quantum mechanics , physics , materials science , composite number , computer science , composite material , embedded system
Natural correlation diagrams have been established to describe hydrogen photoabstraction in ketones and thiones for three different reaction paths ( n x , π x and π c approaches). Their conclusions have been confirmed by ab initio SCF‐CI calculations. This procedure leads to the following conclusions: Energy barriers exist on the potential energy surfaces of all the potentially reactive excited states. The height of these barriers is strongly dependent on the distance separating the hydrogen acceptor and hydrogen donor atoms in the transition state. For the n approach, the reactive channel only involves n π* excited states while, for the π approach, n π* (hydrogen capture by the carbon atom) and ππ* (hydrogen capture by the oxygen or the carbon atom) excited states must also be taken into consideration. A proposal for resolving the ketone‐thione dichotomy is presented on the basis of these results.