Chelate ring geometry,and the metal ion selectivity of macrocyclic ligands. Some recent developments |
| |
Authors: | Robert D. Hancock Arthur E. Martell |
| |
Affiliation: | 1. Department of Chemistry , University of the Witwatersrand , Johannesburg, South Africa;2. Department of Chemistry , Texas A &3. M University , College Station, Texas, USA |
| |
Abstract: | Abstract The idea (Hancock, 1992) that the dominant architectural feature in controlling metal ion selectivity in both open-chain and macro-cyclic ligands is the size of the chelate ring is pursued further. It is shown that when more than one or two six-membered chelate rings are present in the complex of a nitrogen donor macrocycle, the steric requirements of the six-membered chelate ring of a M-N bond length of 1.6 Å and N-M-N angle of 109.5° become particularly severe, and can only be met by a small tetrahedral metal ion. Thus, the ligand 16-aneN4 (1,5,9,13-tetraazacyclohexadecane) forms complexes of low stability with all metal ions studied to date, but a conformer of 16-aneN4 is identified by MM calculation which is predicted to form complexes of high stability with very small tetrahedral metal ions. The question of the M-O bond length and O-M-O angles that will produce minimum strain in chelate rings containing neutral oxygen donor is addressed. The observation (Hay, 1993) that the geometry around an ethereal oxygen coordinated to a metal ion approximates to trigonal planar rather than tetrahedral leads to ideal M-O-C angles of about 126°, which leads to minimum strain energy with much longer M-L lengths in chelate rings containing neutral oxygen donors than neutral nitrogen donors. It is suggested that this fact accounts for the general tendency of crown ethers to form their most stable complexes with potassium out of the alkali metal ions, and also accounts for the very small macrocyclic effect observed in complexes of macrocycles containing mixed nitrogen and oxygen donor groups. The preferred geometry of four-membered chelate rings is discussed, and it is shown that higher coordination numbers of metal ions are associated with four membered chelate rings, and that four membered chelate rings may be used to engineer preference for larger metal ions. Very rigid reinforced chelate rings are discussed, and it is shown that open-chain ligands with reinforced bridges between the donor atoms can display all the thermodynamic and kinetic aspects associated with macrocyclic ligands. |
| |
Keywords: | |
|
|