RELATIONSHIP BETWEEN BASE HYDROLYSIS AND RACEMIZATION AT ASYMMETRIC NITROGEN CENTER IN COBALT(3) COMPLEXES OF 4-(AMINOETHYL)-1,4,7,10-TETRAAZADECANE . PI STABILIZATION IN SN1CB INTERMEDIATE

The structures of sym-Co(trenen)Cl2+, sym-Co(trenen)N32+, and sym-Co(trenen)OH23+ ions [trenen = 4-(aminoethyl)-1,4,7,10-tetraazadecane]:are assigned along with the base hydrolysis and racemization rate constants of the optically active complexes. For the hydrolysis of the chloro complex some racemization occurs in the deprotonated reactant and in the hydroxo product. For the intervening steps, however, the reaction occurs with retention of configuration. This result eliminates for this complex the possibility of an sp2N center Co=N<trans to the leaving group. The general validity of π stabilization of the five-coordinate intermediate is discussed. The results also imply that inversion and conformational interchange are synchronous. © 1969, American Chemical Society. All rights reserved.