Electron transfer reactions to 1-Adamantyl-, 1-Norbornyl Chlorides, and their Oxo Derivatives

DRIANA B. PIERINI, ANA N. SANTIAGO, SIMÓN G. ALLENDE AND D. MARIANO A. VERA

Arkivoc

Arkat USA Inc.

Año: 2003 vol. X p. 477 - 490

1424-6376

The neutral and anionic surfaces of bicyclo[2.2.1]hepta-1-yl chloride (1-chloronorbornane 9), 1- chloroadamantane (4), 2-oxo- (10) and 3-oxo-1-chloronorbornane (11), and 5-chloroadamantan- 2-one (5), were explored at the B3LYP DFT and at the MP2 levels. The studies explain the relative reactivity of these compounds in electron transfer (ET) SRN1 reactions mainly in relation to the position of the oxo substituent on the rigid bridge. The reactivity related to the ET dissociation of the unsubstituted halides 9, 4 and the oxo derivatives 10, 11 can be explained through a concerted-dissociative pathway. On the other hand, an stepwise ET mechanism, with radical anions as intermediates, seems the most adequate reaction path to explain the reactivity of compound 5. Besides, this pathway can also be followed by compounds 10 and 11 under appropriate experimental conditions. The activation energy for the intramolecular-ET through which the radical anions dissociate into radicals follows the order 5 > 11 > 10 in the gas phase and by simulating acetonitrile as polar solvent9), 1- chloroadamantane (4), 2-oxo- (10) and 3-oxo-1-chloronorbornane (11), and 5-chloroadamantan- 2-one (5), were explored at the B3LYP DFT and at the MP2 levels. The studies explain the relative reactivity of these compounds in electron transfer (ET) SRN1 reactions mainly in relation to the position of the oxo substituent on the rigid bridge. The reactivity related to the ET dissociation of the unsubstituted halides 9, 4 and the oxo derivatives 10, 11 can be explained through a concerted-dissociative pathway. On the other hand, an stepwise ET mechanism, with radical anions as intermediates, seems the most adequate reaction path to explain the reactivity of compound 5. Besides, this pathway can also be followed by compounds 10 and 11 under appropriate experimental conditions. The activation energy for the intramolecular-ET through which the radical anions dissociate into radicals follows the order 5 > 11 > 10 in the gas phase and by simulating acetonitrile as polar solvent4), 2-oxo- (10) and 3-oxo-1-chloronorbornane (11), and 5-chloroadamantan- 2-one (5), were explored at the B3LYP DFT and at the MP2 levels. The studies explain the relative reactivity of these compounds in electron transfer (ET) SRN1 reactions mainly in relation to the position of the oxo substituent on the rigid bridge. The reactivity related to the ET dissociation of the unsubstituted halides 9, 4 and the oxo derivatives 10, 11 can be explained through a concerted-dissociative pathway. On the other hand, an stepwise ET mechanism, with radical anions as intermediates, seems the most adequate reaction path to explain the reactivity of compound 5. Besides, this pathway can also be followed by compounds 10 and 11 under appropriate experimental conditions. The activation energy for the intramolecular-ET through which the radical anions dissociate into radicals follows the order 5 > 11 > 10 in the gas phase and by simulating acetonitrile as polar solvent5), were explored at the B3LYP DFT and at the MP2 levels. The studies explain the relative reactivity of these compounds in electron transfer (ET) SRN1 reactions mainly in relation to the position of the oxo substituent on the rigid bridge. The reactivity related to the ET dissociation of the unsubstituted halides 9, 4 and the oxo derivatives 10, 11 can be explained through a concerted-dissociative pathway. On the other hand, an stepwise ET mechanism, with radical anions as intermediates, seems the most adequate reaction path to explain the reactivity of compound 5. Besides, this pathway can also be followed by compounds 10 and 11 under appropriate experimental conditions. The activation energy for the intramolecular-ET through which the radical anions dissociate into radicals follows the order 5 > 11 > 10 in the gas phase and by simulating acetonitrile as polar solventRN1 reactions mainly in relation to the position of the oxo substituent on the rigid bridge. The reactivity related to the ET dissociation of the unsubstituted halides 9, 4 and the oxo derivatives 10, 11 can be explained through a concerted-dissociative pathway. On the other hand, an stepwise ET mechanism, with radical anions as intermediates, seems the most adequate reaction path to explain the reactivity of compound 5. Besides, this pathway can also be followed by compounds 10 and 11 under appropriate experimental conditions. The activation energy for the intramolecular-ET through which the radical anions dissociate into radicals follows the order 5 > 11 > 10 in the gas phase and by simulating acetonitrile as polar solvent9, 4 and the oxo derivatives 10, 11 can be explained through a concerted-dissociative pathway. On the other hand, an stepwise ET mechanism, with radical anions as intermediates, seems the most adequate reaction path to explain the reactivity of compound 5. Besides, this pathway can also be followed by compounds 10 and 11 under appropriate experimental conditions. The activation energy for the intramolecular-ET through which the radical anions dissociate into radicals follows the order 5 > 11 > 10 in the gas phase and by simulating acetonitrile as polar solvent5. Besides, this pathway can also be followed by compounds 10 and 11 under appropriate experimental conditions. The activation energy for the intramolecular-ET through which the radical anions dissociate into radicals follows the order 5 > 11 > 10 in the gas phase and by simulating acetonitrile as polar solvent5 > 11 > 10 in the gas phase and by simulating acetonitrile as polar solvent