期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2004
卷号：101
期号：30
页码：10868-10871
DOI：10.1073/pnas.0404137101
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：Structures of the isomeric adamantanediyl dications C10H142+ and protio-1- and protio-2-adamantyl dications C10H162+ 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 C10H142+. 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 C10H162+ (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. 13C 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.
