Abstract
The enantiomerically pure ligands LRR and LSS (N,N′-bis(-2,2′-bipyridyl-5-yl)carbonyl-(1S/R,2S/R)-(+/−)-1,2-diaminocyclohexane) have been synthesised by linking two 2,2′-bipyridine units by (R,R)- and (S,S)-1,2-diaminocyclohexane respectively. The crystal structure confirmed that the ligand had a twisted orientation between the two chelating units. The reaction of LRR and LSS with Fe(II), Co(III), Cd(II) and Zn(II) afforded dinuclear complexes confirmed by electrospray mass spectroscopy. CD spectroscopy indicated that the chiral diaminocyclohexane conferred helicity to the metal centre giving a dominant triple helicate diastereoisomer, with the LRR ligand giving a ΔΔ-configuration of each metal centre (P helicate) and the LSS ligand a ΛΛ-configuration (M helicate). 1H NMR spectroscopy confirmed a dominant major diastereoisomer with cadmium. The Zn(II) and Cd(II) complexes however were observed to undergo rapid ligand dissociation in solution.
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