A Comparative Nuclear Magnetic Resonance Study of the Solvation of CuClO4 in Binary Mixtures of Acetonitrile with Pyridine and Picolines at 298K

Abstract

63Cu nuclear magnetic resonance (NMR) and viscosity studies of 0:064M CuClO4 solutions have been reported in binary mixtures of acetonitrile (AN) with pyridine (Py) and 2, 3, and 4-picolines (2,3,4-Pic) at 298 K using a Bruker 500 MHz NMR spectrometer and an Ubbelohde viscometer, respectively. Chemical shift d and linewidth D for the 63Cu signals have been recorded referenced to a 0:064M CuClO4 solution in anhydrous AN. The copper quadrupole coupling constants (e 2 Qq=h) have been calculated in all cases. The variation of the d and e 2 Qq=h values as a function of mol fraction of the co-solvent show that all these bases interact with Cu+ more strongly than AN. They replace AN from the Cu+ complexed with AN in the form [Cu(AN)4]+ and form a mixed complex of the type [Cu(AN)4-x(S)x]+ (x=1 - 4) where S stands for the base. At relatively high mole fraction of the co-solvents, the mixed solvated complex gradually changes to a more symmetrical complex of the type [Cu(S)4]+ which remains stable in the solution. The solvating effect of 2-Pic and 4-Pic is observed to be stronger than that of Py and 3-Pic.