SYNTHESES AND COMPARATIVE BASE HYDROLYSIS REACTIONS OF CHLOROCOBALT(III) COMPLEXES OF PENDANT-ARM MACROCYCLIC POLYAMINES AND POLYAMINO ACIDS

Chlorocobalt(III) complexes of the pendant-arm macro cycles 1,4,8,12-t etraazacyclopentadecane-10-carboxylate (2) and 3-tetraazabicyclo[11.2. 2]heptadecane-7-carboxylate (4) have been prepared to complement the k nown complexes of 0-methyl-1,4,8,12-tetraazacyclopentadecan-10-amine ( 1) and 1,5,9,13-tetraazabicyclo[11.2.2]heptadecan-7-amine (3). The pai rs (1),(3) and (2),(4) differ in replacement of pendant amine and meth yl groups in the former pair by a pendant carboxylate group and hydrog en in the latter pair. The macromonocyclic ligands (1) and (2) form ci s-chlorocobalt(III) complexes whereas the macrobicyclic ligands (3) an d (4) (which contain an additional -CH2-CH2-'strap' linking two amines ) form trans-chlorocobalt(III) complexes, defined in terms of location of the pendant donor and the chloride donor. Chloride base hydrolysis kinetics varies With ligand {cis-[Co(1)Cl](2+), k(OH) 6700 dm(3) mol( -1) s(-1); cis-[Co(2)Cl](+), k(OH) 1800 dm(3) mol(-1) s(-1); trans-[Co (3)Cl](2+), k(OH) 3450 dm(3) mol(-1) s(-1); trans-[Co(4)Cl](+), k(OH) 2250 dm(3) mol(-1) s(-1) at 25 degrees C}. Variations in rate constant are tied mainly to variations in activation enthalpy. Chloride hydrol yses occur with retention of configuration, but slow following isomeri zation can lead to products such as trans[Co(2)(OH2)] (ClO4)(2).2H(2)O , which crystallizes in the monoclinic space group P2(1)/c, a 9.581(2) , b 16.214(2), c 14.350(2) Angstrom and beta 94.66(1)degrees. The pend ant carboxylate group and two adjacent secondary amines necessarily oc cupy an octahedral face, with the water molecule bound trans to the pe ndant carboxylate. The four Co-N distances range from 1.981(2) to 2.02 2(3) Angstrom, and along with carboxylate Co-O (1.882(3) Angstrom) and water Co-O (1.934(2) Angstrom) distances are similar to usual distanc es in cobalt(III) complexes.