Intrinsically chiral paddlewheel diruthenium complexes†

IF 2.6 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY CrystEngComm Pub Date : 2024-11-13 DOI:10.1039/D4CE01040J

Isabel Coloma, Santiago Herrero and Miguel Cortijo

{"title":"Intrinsically chiral paddlewheel diruthenium complexes†","authors":"Isabel Coloma, Santiago Herrero and Miguel Cortijo","doi":"10.1039/D4CE01040J","DOIUrl":null,"url":null,"abstract":"A family of heteroleptic paddlewheel diruthenium complexes has been designed to obtain a chiral arrangement of the donor atoms of their equatorial ligands around the metal–metal bond axis. In order to do so, the non-symmetric ligands 2-hydroxy-6-methylpyridinate (hmp) and 2-amino-6-methylpyridinate (amp) were employed to obtain the following four axially chiral compounds: cis-[Ru2Cl(μ-DPhF)2(μ-hmp)(μ-OAc)] (Ruhmp), cis-[Ru2Cl(μ-DPhF)2(μ-amp)(μ-OAc)] (Ruamp), cis-[Ru2Cl(μ-DAniF)2(μ-hmp)(μ-OAc)] (Ru′hmp) and cis-[Ru2Cl(μ-DAniF)2(μ-amp)(μ-OAc)] (Ru′amp) (DPhF = N,N′-diphenylformamidinate, DAniF = N,N′-bis(p-methoxyphenyl)formamidinate). All the compounds were studied by single crystal X-ray diffraction, confirming that a racemic mixture containing only one of the two possible regioisomers was obtained in all cases. A general nomenclature system for naming the full configuration of intrinsically chiral paddlewheel molecules is proposed using the C/A convention. In addition, electronic spectroscopy and cyclic voltamperometry data demonstrate the electronic tunable nature of this new platform. Overall, these results provide a novel example of robust and tunable chirality, which is of potential interest to be further exploited.","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 47","pages":" 6739-6747"},"PeriodicalIF":2.6000,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ce/d4ce01040j?page=search","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"CrystEngComm","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/ce/d4ce01040j","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}

引用次数: 0

Abstract

A family of heteroleptic paddlewheel diruthenium complexes has been designed to obtain a chiral arrangement of the donor atoms of their equatorial ligands around the metal–metal bond axis. In order to do so, the non-symmetric ligands 2-hydroxy-6-methylpyridinate (hmp) and 2-amino-6-methylpyridinate (amp) were employed to obtain the following four axially chiral compounds: cis-[Ru₂Cl(μ-DPhF)₂(μ-hmp)(μ-OAc)] (Ruhmp), cis-[Ru₂Cl(μ-DPhF)₂(μ-amp)(μ-OAc)] (Ruamp), cis-[Ru₂Cl(μ-DAniF)₂(μ-hmp)(μ-OAc)] (Ru′hmp) and cis-[Ru₂Cl(μ-DAniF)₂(μ-amp)(μ-OAc)] (Ru′amp) (DPhF = N,N′-diphenylformamidinate, DAniF = N,N′-bis(p-methoxyphenyl)formamidinate). All the compounds were studied by single crystal X-ray diffraction, confirming that a racemic mixture containing only one of the two possible regioisomers was obtained in all cases. A general nomenclature system for naming the full configuration of intrinsically chiral paddlewheel molecules is proposed using the C/A convention. In addition, electronic spectroscopy and cyclic voltamperometry data demonstrate the electronic tunable nature of this new platform. Overall, these results provide a novel example of robust and tunable chirality, which is of potential interest to be further exploited.