Preparation, properties and crystal structure of two isomers of R,R,S,S- and R,S,R,S-[chloro(1,3,10,12,16,19-hexaazatetracyclo[17,3,1,112,16,04,9]tetracosane)copper(II)]+

Two isomers (R,S,R,S- and R,R,S,S-) of five coordinate complex [Cu(L)Cl]+ have been separated and characterised. These two isomers have significantly different spectrochemical and electrochemical properties. Absorption maximum of R,S,R,S-[Cu(L)Cl]+ shifts to longer wavelength and its reduction potential shifts to more positive direction comparing those of R,R,S,S-[Cu(L)Cl]+. R,S,R,S-[Cu(L)Cl]+ is significantly distorted to trigonal-bipyramidal structure, whereas R,R,S,S-[Cu(L)Cl]+ retains almost square-planar geometry. The average bond distance of Cu–N in basal plane of R,S,R,S-[Cu(L)Cl]+ is longer by 0.024 Å than that of R,R,S,S-[Cu(L)Cl]+, whereas the bond distance of Cu–Cl in former is shorter by 0.200 Å than that in latter. The isolated square-planar complexes of R,R,S,S- and R,S,R,S-[Cu(L)](ClO4)2 are converted to the R,R,S,S- and R,S,R,S-[Cu(L)Cl]+ by the addition of Cl− in nitromethane solution with the rate constants, k=1.70 (±0.02) and 8.31 (±0.07) M−1 s−1, respectively.