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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/25156

Title: Following the Molecular Mechanism of Decarbonylation of Unsaturated Cyclic Ketones Using Bonding Evolution Theory Coupled with NCI Analysis
Authors: Zahedi, Ehsan
Shaabani, Samaneh
Shiroudi, Abolfazl
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. e_zahedi@iau-shahrood.ac.ir
URI: http://hdl.handle.net/1942/25156
DOI: 10.1021/acs.jpca.7b08503
ISI #: 000415141000020
ISSN: 1089-5639
Category: A1
Type: Journal Contribution
Appears in Collections: Research publications

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