Fragmentation of cyclobutoxychlorocarbene: the cyclopropylcarbinyl/cyclobutyl cations revisited

…, F Zheng, LA Johnson, RR Sauers

Index: Moss, Robert A.; Zheng, Fengmei; Johnson, Lauren A.; Sauers, Ronald R. Journal of Physical Organic Chemistry, 2001 , vol. 14, # 7 p. 400 - 406

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Citation Number: 12

Abstract

Abstract Fragmentations of cyclobutoxychlorocarbene (13, k frag= 7.1× 10 5 s− 1) and cyclopropylmethoxychlorocarbene (14, k frag= 7.6× 10 5 s− 1) in MeCN proceed to tight and distinct [R+ OC Cl−] ion pairs, which collapse to different distributions of cyclopropylcarbinyl, cyclobutyl and allylcarbinyl chlorides. B3LYP/6–31G* calculations support these conclusions, affording computed fragmentation activation energies of 6.4 (13) and 3.0 (14) ...