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最简单的弱碱性分子(如SO、CO、N₂O、CO₂等)被固态碳硼烷超酸质子化的特征。

Features of Protonation of the Simplest Weakly Basic Molecules, SO , CO, N O, CO , and Others by Solid Carborane Superacids.

作者信息

Stoyanov Evgenii S, Stoyanova Irina V

机构信息

Vorozhtsov Institute of Organic Chemistry, Siberian Branch of Russian Academy of Sciences, Novosibirsk, 630090, Russia.

Department of Natural Science, National Research University-, Novosibirsk State University, Novosibirsk, 630090, Russia.

出版信息

Angew Chem Int Ed Engl. 2018 Apr 16;57(17):4516-4520. doi: 10.1002/anie.201704645. Epub 2018 Mar 24.

Abstract

An experimental study on protonation of simple weakly basic molecules (L) by the strongest solid superacid, H(CHB F ), showed that basicity of SO is high enough (during attachment to the acidic H atoms at partial pressure of 1 atm) to break the bridged H-bonds of the polymeric acid and to form a mixture of solid mono- LH ⋅⋅⋅An , and disolvates, L-H -L. With a decrease in the basicity of L=CO (via C), N O, and CO (via O), only proton monosolvates are formed, which approach L-H -An species with convergence of the strengths of bridged H-bonds. The molecules with the weakest basicity, such as CO and weaker, when attached to the proton, cannot break the bridged H-bond of the polymeric superacid, and the interaction stops at stage of physical adsorption. It is shown here that under the conditions of acid monomerization, it is possible to protonate such weak bases as CO , N , and Xe.

摘要

一项关于最强固体超强酸H(CHB₁₁F₁₁)使简单弱碱性分子(L)质子化的实验研究表明,SO的碱性足够高(在1个大气压的分压下与酸性H原子结合时),足以打破聚合酸的桥连氢键,并形成固体单质子化产物LH∙∙∙An和溶剂化物L-H-L的混合物。随着L = CO(通过C)、N₂O和CO(通过O)碱性的降低,只形成质子单溶剂化物,随着桥连氢键强度的收敛,它们趋近于L-H-An物种。碱性最弱的分子,如CO及更弱的分子,与质子结合时,无法打破聚合超强酸的桥连氢键,相互作用在物理吸附阶段停止。此处表明,在酸单聚的条件下,有可能使诸如CO₂、N₂和Xe等弱碱质子化。

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