Electronic structure of ring and chain substituted styrenes and their reactivities in the reaction with peroxyl radicals

Autor:	Iosyp O. Opeida, Wolodymyr Ya. Suprun
Rok vydání:	2000
Předmět:	Bond length chemistry.chemical_classification Standard enthalpy of reaction Chain propagation Reaction rate constant Double bond chemistry Enthalpy Physical chemistry Molecule Electronic structure Photochemistry
Zdroj:	Journal of the Chemical Society, Perkin Transactions 2. :1273-1279
ISSN:	1364-5471 1470-1820
DOI:	10.1039/a905404i
Popis:	The structure–reactivity relationship in the chain propagation step of radical chain oxidation of styrenes substituted in the ring (ortho, meta and para) and in the vinyl group (position α and β), the addition of a peroxyl radical to the double bond, was investigated. With the PM3 quantum chemical methods the electronic structure of the reactants, transition state (TS) and the enthalpy of reaction (ΔHRadd) were calculated. A linear correlation between ionisation potentials and energies of the HOMO was observed. The calculated bond lengths and charges on atoms at the reaction centre in the TS in comparison to their reactant values and also the negative ΔHRadd show that the TS is early and charge transfer from molecule to radical dominates in the TS. For styrenes a three parameter correlation of the addition rate constants (k) with the reaction enthalpy, EHOMO and coefficient C1 at the pz atomic orbital of the HOMO of the attacked carbon atom was obtained.
Databáze:	OpenAIRE
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