Carboxymethylated Cage Amines: Coordination and Lactamization
2001-09-22T00:00:00Z (GMT) by
Depending upon the position and degree of substitution, carboxymethyl derivatives of cage amines of the “sarcophagine” (3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane) type vary considerably in the stability of their lactamized forms. For 1,8-diamino-3-carboxymethylsarcophagine, L1, only indirect evidence for some involvement of a lactamized form of its Ni(II) complex has been obtained. Crystal structure determinations for [Cu(H2L1)](NO3)3.5Cl0.5·2.5H2O and [Ni(HL1)]Cl3·3H2O show distorted octahedral coordination of all six endocyclic N-donor atoms in both cases. For related diaminosarcophagine derivatives with either two (1,8; L2) or three (1,1,8; L3) carboxymethyl substituents on the exocyclic N atoms, crystallographic studies have shown a dilactam form for the ligands in their Ni(II) and Cu(II) complexes which is of almost identical conformation to that of the diprotonated “free” ligand in [H2L3][ZnCl4]·6H2O. The lactamized ligands appear to strongly favor square planar four-coordination, and the Co(II) complex of L2 shows a remarkable lack of reactivity toward oxygen. Kinetic studies indicate that the hydrolytic stability of the lactam rings is comparable to that of uncoordinated analogues.