Nitroxyl disulfides, novel intermediates in transnitrosation reactions
Nitroxyl disulfides, novel intermediates in transnitrosation reactions
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DOI：
10.1021/ja029655l
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发表时间：
2003-06-11
影响因子：
15
通讯作者：
Toone, EJ
中科院分区：
文献类型：
--
作者：
Houk, KN;Hietbrink, BN;Toone, EJ
用B3LYP和CBS-QB3方法对转硝化反应的中间体--阴离子RSN(O)SR物种进行了理论计算。该物种类似于与高度扭曲的二硫基配位的氮氧基，并且它在亲核酰基取代方面与中间体有显著不同。为了比较，计算了下列物种的反应：MES-+MeSNO；MeO-+MeONO；MES-+MeSCHO；MeO-+MeOCHO。后两家公司的中间体与前两家公司截然不同。质谱学实验证据与气相中氮氧基二硫的形成相一致。计算了中间体的质子亲和势和氧化还原电势。
A novel anionic RSN(O)SR species, the intermediate in transnitrosation reactions, was explored computationally with B3LYP and CBS-QB3 methods. The species resembles a nitroxyl coordinated to a highly distorted disulficle, and it differs significantly from intermediates in nucleophilic acyl substitution. Reactions of the following species were computed for comparison: MeS- + MeSNO; MeO- + MeONO; MeS- + MeSCHO; MeO- + MeOCHO. The last two have very different intermediates from the first two. Mass spectrometric experimental evidence is presented that is consistent with the formation of a nitroxyl disulficle in the gas phase. The calculated proton affinity and redox potentials of the intermediate are also reported.