ic010049l_si_001.cif (84.61 kB)
Carboxymethylated Cage Amines: Coordination and Lactamization
dataset
posted on 2001-09-22, 00:00 authored by Paul S. Donnelly, Jack M. Harrowfield, Brian W. Skelton, Allan H. WhiteDepending 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.
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carboxymethyl derivativesdiaminosarcophagine derivativescarboxymethyl substituentsdilactam formL 2lactamized ligandscage aminesuncoordinated analoguescrystal structure determinationsKinetic studieslactam ringsNilactamized formClCulactamized formsoctahedral coordinationhydrolytic stabilityexocyclic N atomsfavor square
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