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|Title: ||Following the Molecular Mechanism of Decarbonylation of Unsaturated Cyclic Ketones Using Bonding Evolution Theory Coupled with NCI Analysis|
|Authors: ||Zahedi, Ehsan|
|Issue Date: ||2017|
|Citation: ||JOURNAL OF PHYSICAL CHEMISTRY A, 121(44), p. 8504-8517|
|Abstract: ||The synergetic use of bonding evolution theory (BET) and noncovalent interaction (NCI) analysis allows to obtain new insight into the bond breaking/forming processes and electron redistribution along the reaction path to understand the molecular mechanism of a reaction and recognize regions of strong and weak electron pairing. This viewpoint has been considered for cheletropic extrusion of CO from unsaturated cyclic ketones cyclohepta-3,5-dien-1-one CHD, cyclopent−3-en-1-one CPE, and bicyclo[2.2.1]hept-2-en-7-one BCH by using hybrid functional MPWB1K in conjugation with aug-cc-pVTZ basis set.
Decarbonylation of CHD, CPE, and BCH are nonpolar cyclo-elimination
reactions that are characterized by the sequence of turning points (TPs) as CHD, 1−11-C[CC]C†C†FFFTSC†C†C†−0:HT + CO; CPE, 1−8-CC[C†C†F†]-[FF][FF]FTS[C†C†]−0:BD + CO; and BCH, 1−8 CC[C†C†]F[FF]FTS[C†C†]−0:CD + CO. Breaking of C−C bond between the terminal carbon atoms of diene/triene framework and carbon atom of CO fragment starts at a distance of ca. 1.9−2.0 Å in the vicinity of the transition structure where the transition states are not reached yet. NCI analysis explains that the noncovalent interactions between two fragments appeared after the breaking of C−C bonds.|
|Notes: ||Zahedi, E (reprint author), Islamic Azad Univ, Shahrood Branch, Chem Dept, Shahrood, Iran.
|ISI #: ||000415141000020|
|Type: ||Journal Contribution|
|Appears in Collections: ||Research publications|
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