THERMODYNAMICS OF COPPER(I)-CYCLOOLEFIN COMPLEX FORMATION

A convenient and precise method formeasurement of complex formation constants of Cu(I) has been developed, based on coulometric generation of Cu(I) and potentiometric measurement of the Cu(I) activity in a LiClO4-2-C3H7OH ionic medium. Formation constants and heat of formation values are reported for the 1:1 Cu(I) complexes of a number of cyclic olefins. The logarithmic formation constants of the Cu(I) complexes are linearly related to those of the corresponding Ag(I) complexes. The thermodynamic data for formation of model Cu(I) complexes together with thermodynamic and structural data forthe corresponding Ag(I) complexes indicate that the Cu(I) complex of 2,5-norbornadiene is not chelated. © 1969, American Chemical Society. All rights reserved.