Geometric isomerism in pentacoordinate Cu2+ complexes: equilibrium, kinetic, and density functional theory studies reveal the existence of equilibrium between square pyramidal and trigonal bipyramidal forms for a tren-derived ligand.
A ligand (L1) (bis(aminoethyl)[2-(4-quinolylmethyl)aminoethyl]amine) containing a 4-quinolylmethyl group attached to one of the terminal amino groups of tris(2-aminoethyl)amine (tren) has been prepared, and its protonation constants and stability constants for the formation of Cu(2+) complexes have been determined. Kinetic studies on the formation of Cu(2+) complexes in slightly acidic solutions and on the acid-promoted complex decomposition strongly suggest that the Cu(2+)-L1 complex exists in solution as a mixture of two species, one of them showing a trigonal bipyramidal (tbp) coordination environment with an absorption maximum at 890 nm in the electronic spectrum, and the other one being square pyramidal (sp) with a maximum at 660 nm. In acidic solution only a species with tbp geometry is formed, whereas in neutral and basic solutions a mixture of species with tbp and sp geometries is formed. The results of density functional theory (DFT) calculations indicate that these results can be rationalized by invoking the existence of an equilibrium of hydrolysis of the Cu-N bond with the amino group supporting the quinoline ring so that CuL1(2+) would be actually a mixture of tbp [CuL1(H(2)O)](2+) and sp [CuL1(H(2)O)(2)](2+). As there are many Cu(2+)-polyamine complexes with electronic spectra that show two overlapping bands at wavelengths close to those observed for the Cu(2+)-L1 complex, the existence of this kind of equilibrium between species with two different geometries can be quite common in the chemistry of these compounds. A correlation found between the position of the absorption maximum and the tau parameter measuring the distortion from the idealized tbp and sp geometries can be used to estimate the actual geometry in solution of this kind of complex.
Algarra
Andrés G
AG
Departamento de Ciencia de Materiales e Ingenieria Metalurgica, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, Puerto Real, 11510 Cadiz, Spain.
Basallote
Manuel G
MG
Castillo
Carmen E
CE
Clares
M Paz
MP
Ferrer
Armando
A
García-España
Enrique
E
Llinares
José M
JM
Máñez
M Angeles
MA
Soriano
Conxa
C
D000143:Acids / Q000737:chemistry; D002413:Cations, Divalent / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007536:Isomerism; D007700:Kinetics; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D011522:Protons; D013053:Spectrophotometry
D000143:Acids; D002413:Cations, Divalent; D008024:Ligands; D011522:Protons; D003300:Copper