Non-concerted cope rearrangement

被引：0

作者：

Roth, WR

Gleiter, R

Paschmann, V

Hackler, UE

Fritzsche, G

Lange, H

机构：

[1] Ruhr Univ Bochum, Fak Chem, D-44780 Bochum, Germany

[2] Heidelberg Univ, Inst Organ Chem, D-69120 Heidelberg, Germany

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 1998年 / 1998卷 / 06期

关键词：

diradicals; dioxygen trapping; diradical well; heat of formation; ab initio calculations;

D O I：

10.1002/(SICI)1099-0690(199806)1998:6<961::AID-EJOC961>3.0.CO;2-B

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The observation of practically identical activation parameters for the Cope rearrangement 2-->6 and its "frustrated" counterpart 1-->5 indicates a two-step mechanism for the reaction 2-->6. Direct proof of this interpretation comes from trapping experiments, which demonstrate the intermediate formation of the diradicals 5 and 9. From the temperature and oxygen dependences of the trapping rates, recombination barriers of Delta H-not equal = 11.5 and 6.5 kcal.mol(-1) have been derived for 5-->1 and 9-->6, respectively. These results agree well with ab initio calculations (CASPT2).

引用

页码：961 / 967

页数：7

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[1] 2ND-ORDER PERTURBATION-THEORY WITH A COMPLETE ACTIVE SPACE SELF-CONSISTENT FIELD REFERENCE FUNCTION [J].