Extreme Oxatriquinanes: Structural Characterization of 伪-Oxyoxonium Species with Extraordinarily Long Carbon鈥揙xygen Bonds
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- 作者：Gorkem Gunbas ; William L. Sheppard ; James C. Fettinger ; Marilyn M. Olmstead ; Mark Mascal
- 刊名：The Journal of the American Chemical Society
- 出版年：2013
- 出版时间：June 5, 2013
- 年：2013
- 卷：135
- 期：22
- 页码：8173-8176
- 全文大小：244K
- 年卷期：v.135,no.22(June 5, 2013)
- ISSN：1520-5126
文摘
The first stable 伪-oxyoxonium species have been synthesized and characterized. Strong donation of nonbonding electrons on oxygen into the adjacent 蟽*(C鈥揙+) orbital was predicted by modeling to result in unheard of carbon鈥搊xygen bond lengths. The kinetic stability of the triquinane ring system provides a platform upon which to study these otherwise elusive species, which are evocative of intermediates on the acetalization reaction pathway. Crystallographic analysis of the 伪-hydroxy and 伪-methoxy oxatriquinane triflates reveals 1.658 and 1.619 脜 C鈥揙+ bond lengths, respectively, the former of which is a new record for the C鈥揙 bond.