THEORETICAL EVALUATION OF THE EFFECT OF ELECTRON-WITHDRAWING SUBSTITUENTS ON CARBOCATION STABILITIES - DELOCALIZATION OF CHARGE TO THE CARBONYL AND CYANO GROUPS
THEORETICAL EVALUATION OF THE EFFECT OF ELECTRON-WITHDRAWING SUBSTITUENTS ON CARBOCATION STABILITIES - DELOCALIZATION OF CHARGE TO THE CARBONYL AND CYANO GROUPS
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DOI：
10.1021/ja00326a001
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发表时间：
1984-01-01
影响因子：
15
通讯作者：
HOUK, KN
中科院分区：
文献类型：
--
作者：
DIXON, DA;EADES, RA;HOUK, KN
Theoretical studies of carbocations bearing directly attached electron-withdrawing substituents havebeen completed by using a combination of the approximatePRDDO method and ab initio calculations using different basis sets. All of the theoretical findings agreed quite well with the experimental observations that-cyano and ce-carbonyl groups, which destabilize incipient carbocation centers inductively, provide considerable conjugative stabilization via charge delocalization to the nitrogen of the cyano group or to the oxygen of the carbonyl moiety. A comparison of results obtained by PRDDO and by ab initio calculations with STO-3G, 4-31G, and double-f plus polarization (DZP) basis sets is provided.
