有机主体包封对水溶液中亚硝基苯单体 - 二聚体分布及C - NO键旋转的影响

Organic Host Encapsulation Effects on Nitrosobenzene Monomer-Dimer Distribution and C-NO Bond Rotation in an Aqueous Solution.

作者信息

Varadharajan Ramkumar, Kelley Sarah Ariel, Jayasinghe-Arachchige Vindi M, Prabhakar Rajeev, Ramamurthy Vaidhyanathan, Blackstock Silas C

机构信息

Department of Chemistry, University of Miami, Coral Gables, Miami, Florida 33146, United States.

Department of Chemistry and Biochemistry, The University of Alabama, Tuscaloosa, Alabama 35487-0336, United States.

出版信息

ACS Org Inorg Au. 2021 Dec 22;2(2):175-185. doi: 10.1021/acsorginorgau.1c00043. eCollection 2022 Apr 6.

DOI:10.1021/acsorginorgau.1c00043

PMID:36855459

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9954408/

Abstract

The intermolecular (monomer-dimer equilibrium) and intramolecular (C-NO and C-NMe rotations) dynamics of 4-nitrosocumene () and 4-(,-dimethylamino)nitrosobenzene (), respectively, were found to be controlled by the medium (water) and the host environment (organic capsules and cavitands). The ability of water to shift the equilibrium toward the dimer appears to result from dipolar stabilization of the polar dimer structure and has a resemblance to water's known ability to favor organic cycloaddition reactions. In an aqueous medium, a range of organic hosts selectively include only the nitrosocumene monomer . Encapsulation in the octa acid duplex (OA) selects two monomers rather than a dimer structure. Octa acid encapsulation also results in more restricted intramolecular C-N rotations of the guest .

摘要

结果发现，4-亚硝基异丙苯（）和4-（，-二甲基氨基）亚硝基苯（）的分子间（单体-二聚体平衡）和分子内（C-NO和C-NMe旋转）动力学分别受介质（水）和主体环境（有机胶囊和空穴体）的控制。水将平衡向二聚体方向移动的能力似乎源于极性二聚体结构的偶极稳定作用，并且与水促进有机环加成反应的已知能力相似。在水介质中，一系列有机主体选择性地只包含亚硝基异丙苯单体。在八酸双链体（OA）中包封选择了两个单体而不是二聚体结构。八酸包封还导致客体分子内C-N旋转受到更大限制。