𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Theoretical study on the gas-phase reactivity of halogenated alkylperoxyl radicals toward alkenes

✍ Scribed by S. El-Taher

Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
273 KB
Volume
71
Category
Article
ISSN
0020-7608

No coin nor oath required. For personal study only.

✦ Synopsis

The electrophilic additions of hydroperoxyl HO , alkylperoxyl RO , 2 2 and halogenated alkylperoxyl radicals to ethylene were studied using the AM1 and PM3 semiempirical MO methods at the SCFrUHF level. Reactantlike transition states were Ε½ U . predicted for the title additions. The AM1 activation enthalpies ⌬ H were found to be f increased in the order HO Ψ’ -CH O Ψ’ -C H O Ψ’i-C H O Ψ’ . The reactivity of an 2 3 2 2 5 2 3 7 2 alkylperoxyl radical toward ethylene was found to be increased as the degree of halogen substitution on the alkyl group increased. A good correlation was established between ⌬ H U and the Taft polar substituent constants, *. The Evans᎐Polanyi correlation f between ⌬ H U and ⌬ H T was justified and the validity of the Hammond postulate was f r indicated. The calculated results were compared with the available experimental findings.

πŸ“œ SIMILAR VOLUMES

High reactivity of hexafluoro acetone to
High reactivity of hexafluoro acetone toward criegee intermediates in the gas-phase ozonolysis of simple alkenes
✍ Osamu Horie; Christian SchΓ€fer; Geert K. Moortgat πŸ“‚ Article πŸ“… 1999 πŸ› John Wiley and Sons 🌐 English βš– 178 KB πŸ‘ 2 views

Hexafluoro acetone CF 3 COCF 3 has been shown to react rapidly with the CH 2 OO, CH 3 CHOO, and (CH 3 ) 2 COO intermediates that are formed in the ozonolysis of C 2 H 4 , trans-2-C 4 H 8 , and 2,3-dimethyl-2-butene, respectively, and to form products tentatively assigned to the corresponding seconda

Theoretical studies on the gas-phase nuc
Theoretical studies on the gas-phase nucleophilic substitution reactions of benzyl chlorides with phenoxides and thiophenoxides
✍ Wang Ki Kim; Wang Sun Ryu; In-Suk Han; Chang Kon Kim; Ikchoon Lee πŸ“‚ Article πŸ“… 1998 πŸ› John Wiley and Sons 🌐 English βš– 167 KB πŸ‘ 2 views

Gas-phase nucleophilic substitution reactions of Y-benzyl chlorides with X-phenoxide and Xthiophenoxide nucleophiles were investigated theoretically using the PM3 semi-empirical MO method. The Leffler-Grunwald rate-equilibrium and BrΓΈnsted correlations predict that the degree of bond formation in th

ChemInform Abstract: Experimental and Th
ChemInform Abstract: Experimental and Theoretical Studies on the Reactivities of Partially and Fully Fluorinated Primary Alkyl Radicals.
✍ M. D. BARTBERGER; W. R. JUN. DOLBIER; J. LUSZTYK; K. U. INGOLD πŸ“‚ Article πŸ“… 2010 πŸ› John Wiley and Sons βš– 26 KB πŸ‘ 1 views

Experimental and Theoretical Studies on the Reactivities of Partially and Fully Fluorinated Primary Alkyl Radicals. -The absolute rate constants for the hydrogen abstraction from Bu3SnH by a number of partially-fluorinated and fully-fluorinated alkyl radicals are measured. The rate data are compare

A gas-phase study of ligand effects on t
A gas-phase study of ligand effects on the reactivity of organometallic distonic ion Fe(p-benzyne)+Λ™
✍ Young C. Xu; Quan Chen; Sara K. Poehlein; Ben S. Freiser πŸ“‚ Article πŸ“… 1999 πŸ› John Wiley and Sons 🌐 English βš– 91 KB πŸ‘ 2 views

This paper reports a gas-phase study of ligand effects on the reactivity of the organometallic distonic ion Fe(p-benzyne) Á . New organometallic distonic ions are generated by introducing a benzene ligand onto the metal center of Fe(p-benzyne) Á . We were interested in whether the reactivity of the