ROLE OF OXONIUM, SULFONIUM, AND CARBOXONIUM DICATIONS IN SUPERACID-CATALYZED REACTIONS
ROLE OF OXONIUM, SULFONIUM, AND CARBOXONIUM DICATIONS IN SUPERACID-CATALYZED REACTIONS
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DOI：
10.1021/ja00057a009
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发表时间：
1993-02-24
影响因子：
15
通讯作者：
OLAH, GA
中科院分区：
文献类型：
--
作者：
HARTZ, N;RASUL, G;OLAH, GA
用从头算分子轨道理论计算了一系列甲基取代的氧鎓、锍和羧鎓双阳离子（二-O-质子化羰基化合物）的能量、电子结构、气相质子亲合势和等键构型（Δ H 0 iso）.在计算能量学的基础上，估算了质子亲合能和分解能垒。讨论了双阳离子超亲电体在一些超强酸催化反应中的作用。
Energies, electronic structures, gas-phase proton affinities, and isodesmic enthalpies (DELTAH0iso) of a series of methyl-substituted oxonium and sulfonium dications and carboxonium dications (di-O-protonated carbonyl compounds) were calculated using ab initio molecular orbital theory. On the basis of computed energetics, the proton affinities and decomposition barriers were also estimated. The role of dicationic superelectrophiles in a number of superacid-catalyzed reactions is discussed.