Isomerization pathway of a C–C sigma bond in a bis(octaazamacrocycle)dinickel(II) complex activated by deprotonation: a DFT study

IF 16.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Accounts of Chemical Research Pub Date : 2024-03-13 DOI:10.1007/s00214-024-03100-5

Ingrid Jelemenska, Michal Zalibera, Peter Rapta, Anatoly A. Dobrov, Vladimir B. Arion, Lukas Bucinsky

{"title":"Isomerization pathway of a C–C sigma bond in a bis(octaazamacrocycle)dinickel(II) complex activated by deprotonation: a DFT study","authors":"Ingrid Jelemenska, Michal Zalibera, Peter Rapta, Anatoly A. Dobrov, Vladimir B. Arion, Lukas Bucinsky","doi":"10.1007/s00214-024-03100-5","DOIUrl":null,"url":null,"abstract":"The anti (a) to syn (s) isomerization pathway of the deprotonated form of the dimer with two nickel(II) 15-membered octaazamacrocyclic units connected via a carbon–carbon (C–C) σ bond was investigated. For the initial anti (a) structure, a deprotonation of one of the bridging (sp3 hybridized) carbon atoms is suggested to allow for an a to s geometry twist. A 360° scan around the bridging C–C dihedral angle was performed first to find an intermediate geometry. Subsequently, the isomerization pathway was explored via individual steps using a series of mode redundant geometry optimizations (internal coordinates potential energy surface scans) and geometry relaxations leading to the s structure. The prominent geometries (intermediates) of the isomerization pathway are chosen and compared to the a and s structures, and geometry relaxations of the protonated forms of selected intermediates are considered.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4000,"publicationDate":"2024-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Accounts of Chemical Research","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1007/s00214-024-03100-5","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}

引用次数: 0

Abstract

The anti (a) to syn (s) isomerization pathway of the deprotonated form of the dimer with two nickel(II) 15-membered octaazamacrocyclic units connected via a carbon–carbon (C–C) σ bond was investigated. For the initial anti (a) structure, a deprotonation of one of the bridging (sp³ hybridized) carbon atoms is suggested to allow for an a to s geometry twist. A 360° scan around the bridging C–C dihedral angle was performed first to find an intermediate geometry. Subsequently, the isomerization pathway was explored via individual steps using a series of mode redundant geometry optimizations (internal coordinates potential energy surface scans) and geometry relaxations leading to the s structure. The prominent geometries (intermediates) of the isomerization pathway are chosen and compared to the a and s structures, and geometry relaxations of the protonated forms of selected intermediates are considered.

Abstract Image

查看原文本刊更多论文

双(八氮杂环)二镍(II)复合物中由去质子化激活的 C-C sigma 键的异构化途径：DFT 研究

研究了含有两个通过碳碳（C-C）σ键连接的 15 元八氮杂环单元的镍(II)二聚体的去质子化形式的反（a）到合（s）异构化途径。对于最初的反 (a) 结构，建议对其中一个桥接（sp3 杂化）碳原子进行去质子化处理，以实现从 a 到 s 的几何扭曲。首先围绕桥接 C-C 二面角进行 360° 扫描，以找到中间几何结构。随后，通过一系列模式冗余几何优化（内部坐标势能面扫描）和几何松弛，探索了通向 s 结构的单步异构化途径。我们选择了异构化途径中的主要几何结构（中间体），并将其与 a 和 s 结构进行了比较，还考虑了所选中间体质子化形式的几何松弛。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Accounts of Chemical Research 化学-化学综合

CiteScore

31.40

自引率

1.10%

发文量

312

审稿时长

2 months

期刊介绍： Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.