SUBSTITUTION-REACTIONS OF 5-COORDINATE COMPLEXES .1. FORMATION AND AQUATION KINETICS OF THE (ACIDO) (RAC-5,5,7,12,12,14-HEXAMETHYL-1,4,8,11-TETRAAZACYCLOTETRADECANE)COPPER(II) (BLUE) CATION

[[abstract]]Rate constants for the formation (kf) and the aquation (kaJ of seven different (acido)(rac-5,5,7,12,12,14-hexamethyl- 1,4,8,1l-tetraazacyclotetradecane)copper(II) (blue) complexes, [Cu(tet b)Y(blue)]+ (Y- = C1-, Br-, I-, SCN-, N3-, O,CMe-, CN-), have been determined between 15.0 and 40.0 OC at p = 0.10 M (NaNO, + Nay) by the stopped-flow method. These complexes present a trigonal-bipyramidal geometry with Y- or H20 in equatorial position. The equilibrium constants, Ky, for the complexation reactions of [Cu(tet b)(H20)(blue)]z+ with these anions obtained by spectrophotometric measurements under equilibrium conditions are in excellent agreement with kinetically determined values (kf/k,,). A graph of log kf against log Ky gives a slope of 0.85. The kinetic results are consistent with an associative-interchange, I,, mechanism[[fileno]]2010337010029[[department]]化學