Coordination of Cu2+ ions to C2 symmetric pseudopeptides derived from valine.
The acid-base and coordination properties of a family of pseudopeptidic ligands with C(2) symmetry derived from valine (4a-e) have been studied using a variety of techniques as a model for metal coordination in peptides and proteins. The Cu(2+) cation has been selected for coordination studies, although, for comparison, some results for Zn(2+) are also presented. Good agreement has been obtained between the results obtained by potentiometric titrations, spectroscopic analysis, and mass spectrometry (ESI) studies. These results highlight the potential for the use of ESI MS for characterizing the nature of the complex species formed. Clearly, the Cu(2+) complexes are much more stable than the Zn(2+) complexes. While the role of the aliphatic spacer seems to be very minor in the case of the Zn(2+) complexes, revealing the ability of this cation to accommodate different coordination environments, this role is critical in the case of Cu(2+). Different complexes with 1:1 or 2:2 Cu(2+):L stoichiometries can be formed according to the length of the spacer and the basicity of the media. This is fully illustrated by the resolution of the X-ray structures of two different Cu(2+) complexes corresponding to the ligands containing a spacer with two methylene groups (ligand 4a, complex 6a [Cu(2)(H(-1)L)(2)](ClO(4))(2) with a 2:2 stoichiometry) and a propylene spacer (4b, complex 5b [CuH(-2)L] x CH(3)CH(2)OH with a 1:1 stoichiometry).
Blasco
Salvador
S
Instituto de Ciencia Molecular (ICMOL), Departamento de Química Inorgánica, Universidad de Valencia, 46980 Paterna (Valencia), Spain.
Burguete
M Isabel
MI
Clares
M Paz
MP
García-España
Enrique
E
Escorihuela
Jorge
J
Luis
Santiago V
SV
D002413:Cations, Divalent / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D011522:Protons; D021241:Spectrometry, Mass, Electrospray Ionization; D014633:Valine / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry
D002413:Cations, Divalent; D056831:Coordination Complexes; D011522:Protons; D003300:Copper; D014633:Valine; D015032:Zinc