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/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.
Published Version
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