AlIII ion complexes of saccharic acid and mucic acid: a solution and solid-state study.
The Al(III)-binding abilities of two aldaric acids, D-saccharic acid and mucic acid (the neutral form is denoted as H(2)L), were studied in solution by means of pH potentiometric, (1)H and (13)C NMR, and ESI-MS techniques. The most probable conformations and isomeric binding modes of the complexes formed in solution were determined by density functional theory (DFT) calculations. A solid D-saccharic acid complex K(2)[[Al(LH(-2))(H(2)O)](2)].H(2)O was isolated and crystallographically characterised. The two alcoholic hydroxy groups alpha to the terminal COO(-) groups were found to take part in the coordination, but in different ways. One of them coordinates in a bridging mode. Detailed ESI-MS and NMR studies proved that the complex retains its structure in solution. However, depending on the ligand and the pH, such complexes may exist in two isomeric forms. DFT calculations on the ion [[Al(LH(-2))(H(2)O)](2)](2-) revealed that several orbitals participate in stabilizing the dimeric arrangement.
Biocoordination Chemistry Research Group, of the Hungarian Academy of Sciences, University of Szeged, PO Box 440, 6701 Szeged, Hungary.
Andrea
A
Lakatos
Roberta
R
Bertani
Tamas
T
Kiss
Alfonso
A
Venzo
Maurizio
M
Casarin
Franco
F
Benetollo
Paolo
P
Ganis
Donata
D
Favretto
D000535:Aluminum / Q000737:chemistry*; D001205:Ascorbic Acid / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006863:Hydrogen-Ion Concentration; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012996:Solutions / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D013400:Sugar Acids / Q000737:chemistry*
D009942:Organometallic Compounds; D012996:Solutions; D013400:Sugar Acids; D000535:Aluminum; C000090:galactaric acid; D001205:Ascorbic Acid