SYNTHESIS AND CHARACTERIZATION OF 1-(2H-TETRAZOL-5-YL)-1,4,7,10-TETRAAZACYCLODODECANE AND ITS Zn(II),Ni(II),AND Cu(II) COMPLEXES

摘要

As part of an ongoing effort to develop new metal complexes of tetraazamacrocycles with novel properties in coordination or functionalization we report here the synthesis of a new derivative of 1,4,7,10-tetraazacyclododecane (cyclen) with a tetraazole moiety directly bound to the azamacrocycle.The new ligand was obtained by reaction with cyanogen bromide giving the cyanamide,followed by a [2+3] cycloaddition with NaN3 to yield the tetraazole.The ligand and its Zn(II),Ni(II),and Cu(II) complexes were fully characterized by analytical methods.X-ray structure analysis of the Ni(II) compound shows the formation of a stable dimer by coordination of each of the two tetraazole substituents to the neighboring metal cation.Potentiometric titrations of the metal complexes indicate a possible conversion of the monomer to the dimeric structure in solution and show the pK_a of the NH-atom on the tetraazole substituent to be between 4.03 and 5.3 depending on the metal ion coordinated by cyclen.