Octahedral cobalt(III) complexes of the chloropentammine type. XXI. The preparation, properties, and reactions of some Chloro(amine)bis(ethylenediamine)cobalt(III) salts containing unidentate glycinenitrile and glycinamide as influencing ligands

Abstract

Salts of one isomeric series of chloro(amine)bis(ethylenediamine)cobalt(111) type of cations have been prepared from trans-dichlorobis(ethy1enediamine)-cobalt(111) chloride by replacing one of its chloro ligands with either glycinenitrile or glycinamide. These complexes have been assigned a cis-configuration on the basis of spectral observations. For the glycinenitrile system, the cis-chloro(cyano-methylamine)bis(ethylenediamine)cobalt(111) cation rearranges to the trans-chloro(aminoacetonitrile) isomer in aqueous solution at rates very much higher than those for the aquation of both forms. This isomerization is retarded by acid and accelerated by base. The kinetics of base hydrolysis are also reported. On the other hand, for the glycinamide system, the corresponding isomerization proceeds at rates comparable to those of chloride release, the latter leading to the formation of the chelated N,O-glycinamidebis(ethylenediamine)cobalt(111) species. Consequently, it has not been possible to isolate the other linkage isomer in the pure state. Furthermore, although the aquo(glycinamide)bis(ethylenediamine)cobalt(111) species is not formed in non-basic spontaneous chloride release, its hydroxo counterpart can be readily obtained by base hydrolysis. The mechanistic implications of these observations are discussed.