The R3O+···H+ hydrogen bond: toward a tetracoordinate oxadionium(2+) ion.
The R3O+···H+ hydrogen bond: toward a tetracoordinate oxadionium(2+) ion.
复制标题
DOI：
10.1021/ja209942s
复制
发表时间：
2012-01-11
影响因子：
15
通讯作者：
Reed, Christopher A.
中科院分区：
文献类型：
--
作者：
Stoyanov, Evgenii S.;Gunbas, Gorkem;Hafezi, Nema;Mascal, Mark;Stoyanova, Irini V.;Tham, Fook S.;Reed, Christopher A.
氧杂三喹是三环氧鎓离子，已知其与简单的烷基氧鎓盐相比具有显著的溶剂分解稳定性。它们的刚性半球形结构在三个稠合的五元环的顶点处呈现氧。虽然像这些三价氧物种已经在文献中得到了很好的描述，但氧进入第四共价键合关系的能力已经在理论上得到了考察，并通过在超强酸介质中进行的某些反应的结果得到了暗示，但从未通过表征稳定的、持久的R3 OH ++或R4 O ++离子来建立。在这项研究中，oxatriquinane氧的亲核性进行了评估，首先通过一系列的质子化研究，使用布朗斯台德超强酸H（CHB 11 Cl 11）在固态和液体HCl溶液中。还研究了氧杂三喹氧与桥连碳阳离子的相互作用。一个强有力的情况下，可以为H（CHB 11 Cl 11）和oxatriquinane使用红外光谱之间的氢键的发生。在最强制质子化条件下，氧杂三喹环被裂解，得到桥接的双阳离子质子化四氢呋喃-碳正离子。
Oxatriquinanes are tricyclic oxonium ions which are known to possess remarkable solvolytic stability compared to simple alkyl oxonium salts. Their rigid, hemispherical structure presents an oxygen at the apex of three fused five-membered rings. While trivalent oxygen species like these have been well described in the literature, the ability of oxygen to enter into a fourth covalent bonding relationship has been visited in theory and suggested by the outcome of certain reactions conducted in superacidic media, but has never established by the characterization of a stable, persistent R3OH++ or R4O++ ion. In this study, the nucleophilicity of the oxatriquinane oxygen was evaluated first by a series of protonation studies using the Brønsted superacid H(CHB11Cl11) both in the solid state and in liquid HCl solution. The interaction of the oxatriquinane oxygen with a bridging carbocation was also examined. A strong case could be made for the occurrence of hydrogen bonding between H(CHB11Cl11) and oxatriquinane using IR spectroscopy. Under the most forcing protonation conditions, the oxatriquinane ring is cleaved to give a bridged, dicationic protonated tetrahydrofuran-carbenium ion.
登录
查看更多内容
DOI：
10.1002/anie.199307673
发表时间：
1993-06-01
期刊：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH
影响因子：
--
作者：
OLAH, GA
通讯作者：
OLAH, GA
影响因子：
--
作者：
Meerwein, H;Hinz, G;Pfeil, E
通讯作者：
Pfeil, E
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD
影响因子：
2.8
作者：
Jutzi, P;Müller, C;Stammler, HG
通讯作者：
Stammler, HG
影响因子：
15
作者：
HARTZ, N;RASUL, G;OLAH, GA
通讯作者：
OLAH, GA