In pursuit of natural occurring chiral dienes {(R/S)-carvone} as bidentate ligands for coordination to rhodium(I).

IF 2.2 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Coordination Chemistry Pub Date : 2025-01-10 eCollection Date: 2025-01-01 DOI:10.1080/00958972.2024.2448520

Zaskia Bezuidenhout, Andreas Roodt

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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-[Rh^I(SCar)Cl]₂ (IA/B) and mu-[Rh^I(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-[Rh^I(SCar)Cl]₂ (IA), Anti-mu-[Rh^I(SCar)Cl]₂ (IB), and Syn-mu-[Rh^I(RCar)Cl]₂ (IIA, Anti-mu-[Rh^I(RCar)Cl]₂ (IIB), respectively (based on the relative orientation of the carvone ring, oxo and methyl groups). Principal differences between the IA/IIA vs IB/IIB complexes in the solid state include the relative orientation of the two carvones, inducing a significant distortion in the µ ²-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.

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来源期刊

Journal of Coordination Chemistry 化学-无机化学与核化学

CiteScore

3.60

自引率

10.50%

发文量

171

审稿时长

3.2 months

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.