BOND-DISSOCIATION ENERGIES IN DMSO RELATED TO THE GAS-PHASE
BOND-DISSOCIATION ENERGIES IN DMSO RELATED TO THE GAS-PHASE
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DOI：
10.1021/ja00026a012
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发表时间：
1991-12-18
影响因子：
15
通讯作者：
ZHANG, XM
中科院分区：
文献类型：
--
作者：
BORDWELL, FG;CHENG, JP;ZHANG, XM
估算了（a）14种烃中的苄基或烯丙基H-C键，（B）12种含一个或多个杂原子的烃中的酸性H-C键，（c）5种含氮酸以及苯硫酚和苯酚中的H-N键的均裂键离解能。对于文献气相值可用的18种化合物，除三种（Ph 3CH、PhNH 2和PhOH）外，所有化合物均观察到在+/- 2 kcal/mol范围内的一致性。对于Ph 3CH和PhNH 2，文献值显示出错误。对于17种化合物中酸性H-A键的溴化二苯醚，根据对三种或三种以上衍生物（其中远程取代基位于母体化合物的苯环上）的溴化二苯醚估计值，确定了+/- 2千卡/摩尔或更好的误差限度。总之，32种化合物的酸性H-A键的BDE已确定为+/- 2 kcal/mol或更好。
Estimates have been made of the homolytic bond dissociation energies (BDEs) for (a) the benzylic or allylic H-C bonds in 14 hydrocarbons, (b) the acidic H-C bonds in 12 hydrocarbons containing one or more heteroatoms, and (c) the H-N bonds in five nitrogen acids as well as thiophenol and phenol. For the 18 compounds where literature gas-phase values were available, agreement to within +/- 2 kcal/mol was observed for all but three (Ph3CH, PhNH2, and PhOH). For Ph3CH and PhNH2, the literature values were shown to be in error. For the BDEs of the acidic H-A bonds in 17 compounds, error limits of +/- 2 kcal/mol, or better, were established from BDE estimates made for three or more derivatives in which remote substituents were placed on the benzene ring of the parent compound. In all, the BDEs of the acidic H-A bonds of 32 compounds have been established to +/- 2 kcal/mol or better.