Circular dichroism (CD) spectra of individual mixed-ligand copper(I1) complexes of 1,3-dicarbonyl compounds, (1s)-or (lR)-3-hydroxymethylene camphor, (1S)-3-trifluoroacetyl camphor, or (lR)-2-hydroxymethylene menthone, and a-amino acids, alanine, valine, proline, or their N-alkyl derivatives, were calculated from CD spectra of equilibrium solutions containing the above constituents in methanol or ethylene dichloride. Diastereomeric mixed-ligand complexes incorporating identical dicarbonyl but enantiomeric N-alkyl-aamino acid ligands exhibit quasi-enantiomeric CD spectra. Unsubstituted amino acids, on the contrary, will make no decisive contributions to the net optical activity spectrum of the mixed-ligand complexes. Formation constants of diastereomeric mixed-ligand complexes have been calculated from data on disproportionation of the latter into corresponding equally paired complexes. Enantioselectivity was demonstrated to amount to up to 700 cal/mol. Possible steric structures of mixed-ligand complexes are discussed. o 1993 Wiey-Liss, Inc.KEY WORDS: enantioselectivity, mixed-ligand copper complexes, formation constants, amino acids, 1,3-dicarbonyl compounds, circular dichroismEnantioselective effects in labile coordination compounds play an important role in a number of biological systems. They also form the basis of ligand-exchange chromatographic resolution of racemic compounds. In both cases, there is great interest not in homoligand but rather heteroligand (mixedligand) complexes which bear two ligands that differ in their chemical nature. With this in view, potentiomeric investigations of enantioselectivity in heteroligand amino acid complexes have been carried outla and attempts have been made to relate these results with chromatographic data.3While examining enantioselective effects in nonaqueous media, absorption and circular dichroism (CD) spectra4 appeared to be more convenient as compared to the traditional potentiometric titration.In this paper, we present results of studies on enantioselectivity in heteroligand complexes of copper(I1) ions that contain 1,s-dicarbonyl and amino acid ligands by CD spectroscopy.Another subject of present interest is the shapes of the CD spectra of heteroligand complexes and their dependence on the type of solvent. This provides important information on the structural peculiarities of these complexes.
RESULTS AND DISCUSSION
CD Spectra of Heteroligand ComplexesThe object of the investigation was the square-planar cop- phor, or (lR)-2-hydroxymethylene menthone, the latter designated OMC, TFC, and OMM, respectively. Complexes of copper bearing these ligands are kinetically labile, and mixing solutions of two individual complexes, CuA, and CUB,, produces the heteroligand complex, CuAB, according to the equilibrium (1):Both the equilibrium constant K and spectral characteristics of the heteroligand complex CuAB can be calculated from the characteristics of a series of equilibrium mixtures.As Figure 1 portrays, the contributions of two ligands to CD spectra of the fi...