{"title":"In pursuit of natural occurring chiral dienes {(R/S)-carvone} as bidentate ligands for coordination to rhodium(I).","authors":"Zaskia Bezuidenhout, Andreas Roodt","doi":"10.1080/00958972.2024.2448520","DOIUrl":null,"url":null,"abstract":"<p><p>Bis-rhodium-<i>mu</i>-chlorido dinuclear complexes with natural occurring limonene-type enantiomeric diene nucleophiles, (S)- and (R)-carvone [<b>S</b>Car and <b>R</b>Car], are presented and their single crystal structures reported. Utilizing the diolefinic bonds of the carvones, <i>mu</i>-[Rh<sup>I</sup>(<b>S</b>Car)Cl]<sub>2</sub> (<b>IA/B</b>) and <i>mu</i>-[Rh<sup>I</sup>(<b>R</b>Car)Cl]<sub>2</sub> (<b>IIA/B</b>) were obtained in ca. 80% yields in clean reactions with reactant RhCl<sub>3</sub>(H<sub>2</sub>O)<sub>x</sub>. The \"structured\" chiral nanomaterials (<b>IA/B</b> and <b>IIA/<i>B</i> </b>><b> </b>1.1 nm) crystallize as two independent, dinuclear chiral molecules <i>Syn-mu</i>-[Rh<sup>I</sup>(<b>S</b>Car)Cl]<sub>2</sub> (<b>IA</b>), <i>Anti-mu</i>-[Rh<sup>I</sup>(<b>S</b>Car)Cl]<sub>2</sub> (<b>IB</b>), and <i>Syn-mu</i>-[Rh<sup>I</sup>(<b>R</b>Car)Cl]<sub>2</sub> (<b>IIA</b>, <i>Anti-mu</i>-[Rh<sup>I</sup>(<b>R</b>Car)Cl]<sub>2</sub> (<b>IIB</b>), respectively (based on the relative orientation of the carvone ring, oxo and methyl groups). Principal differences between the <b>IA/IIA</b> <i>vs</i> <b>IB/IIB</b> complexes in the solid state include the relative orientation of the two carvones, inducing a significant distortion in the <i>µ</i> <sup>2</sup>-Rh<sub>2</sub>Cl<sub>2</sub> core, with the dihedral angles of 49.7(1)°/49.73(6)° in <b>IA/IIA</b> (<i>Syn-mu</i> geometry), versus 23.8(1)°/24.00(6)° in <b>IB/IIB</b> (<i>Anti-mu</i> geometry), respectively. The presence of the two structurally independent complexes in the solid state is also inferred from <sup>1</sup>H NMR spectra.</p>","PeriodicalId":15421,"journal":{"name":"Journal of Coordination Chemistry","volume":"78 1-3","pages":"208-224"},"PeriodicalIF":2.2000,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11854040/pdf/","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Coordination Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1080/00958972.2024.2448520","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/1/1 0:00:00","PubModel":"eCollection","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Bis-rhodium-mu-chlorido dinuclear complexes with natural occurring limonene-type enantiomeric diene nucleophiles, (S)- and (R)-carvone [SCar and RCar], are presented and their single crystal structures reported. Utilizing the diolefinic bonds of the carvones, mu-[RhI(SCar)Cl]2 (IA/B) and mu-[RhI(RCar)Cl]2 (IIA/B) were obtained in ca. 80% yields in clean reactions with reactant RhCl3(H2O)x. The "structured" chiral nanomaterials (IA/B and IIA/B>1.1 nm) crystallize as two independent, dinuclear chiral molecules Syn-mu-[RhI(SCar)Cl]2 (IA), Anti-mu-[RhI(SCar)Cl]2 (IB), and Syn-mu-[RhI(RCar)Cl]2 (IIA, Anti-mu-[RhI(RCar)Cl]2 (IIB), respectively (based on the relative orientation of the carvone ring, oxo and methyl groups). Principal differences between the IA/IIAvsIB/IIB complexes in the solid state include the relative orientation of the two carvones, inducing a significant distortion in the µ2-Rh2Cl2 core, with the dihedral angles of 49.7(1)°/49.73(6)° in IA/IIA (Syn-mu geometry), versus 23.8(1)°/24.00(6)° in IB/IIB (Anti-mu geometry), respectively. The presence of the two structurally independent complexes in the solid state is also inferred from 1H NMR spectra.
期刊介绍：
The Journal of Coordination Chemistry publishes the results of original investigations of coordination complexes, loosely defined as the interactions of organic or inorganic ligands with metal centres. Original investigations may involve syntheses, structures, physical and chemical properties, kinetics and mechanisms of reactions, calculations and applications of coordination compounds. The applications may involve bioinorganic, organometallic, catalytic, solid state/materials, coordination chemistry of nanostructured surfaces and medicinal studies.
The Journal publishes original manuscripts, communications and reviews. Original manuscripts are expected to provide a clear contribution to the advance of coordination chemistry. Communications are short manuscripts with an urgency that requires rapid publication. Reviews are welcome in all areas of coordination chemistry and may focus on the metal, ligand or applications. Reviews of emerging areas of coordination chemistry should be developed fully from the basics, carefully relating the topic to the field in general. Reviews of well established subjects should collect developments from the literature and take a critical view of recent work.
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