Density functional theory study of adamantanediyl dications C10H142+ and protio-adamantyl dications C10H162+.
Density functional theory study of adamantanediyl dications C10H142+ and protio-adamantyl dications C10H162+.
复制标题
金刚烷二基二甲基化合物C10H142和原子金刚烷基二甲基化合物C10H162的密度泛函理论研究。
DOI：
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发表时间：
2004
影响因子：
11.1
通讯作者：
G. Prakash
中科院分区：
文献类型：
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作者：
G. Rasul;G. Olah;G. Prakash
采用密度泛函理论（DFT）方法，在B3 LYP/6- 31 G ** 水平上，研究了金刚烷二基二价阳离子C（10）H（14）（2+）和金刚烷二基二价阳离子C（10）H（16）（2+）的结构.在C（10）H（14）（2+）的势能面上发现了4个极小结构1b-e。发现具有两个桥头叔碳阳离子中心的1，3-金刚烷二基二价阳离子1b是最稳定的结构。在C（10）H（16）（2+）（质子化金刚烷阳离子）的势能面上，发现了5种最小结构2b-f。每个结构都包含一个两电子三中心键。C-C质子化的1-金刚烷基二价阳离子2f被表征为最稳定的结构。(13)C用含规范原子轨道密度泛函理论和含规范原子轨道自洽场方法计算了这些结构的NMR化学位移。
Structures of the isomeric adamantanediyl dications C(10)H(14)(2+) and protio-1- and protio-2-adamantyl dications C(10)H(16)(2+) were investigated by using the density functional theory (DFT) method at the B3LYP/6-31G** level. Four structures, 1 b-e, were found to be minima on the potential energy surface of C(10)H(14)(2+). The 1,3-adamantanediyl dication 1b with two bridgehead tertiary carbocationic centers was found to be the most stable structure. On the potential energy surface of C(10)H(16)(2+) (protonated adamantly cation), five structures, 2 b-f, were found to be minima. Each of the structure contains a two-electron, three-center bond. The C-C protonated 1-adamantyl dication, 2f, was characterized as the most stable structure. (13)C NMR chemical shifts of the structures were also calculated by using gauge-including atomic orbital-density functional theory and gauge-including atomic orbital-self-consistent field methods.