COORDINATION CHEMISTRY OF AMINOPHOSPHONIC AND AMINOPHOSPHINIC ACIDS

       Aminoalkylphosphonic or phosphinic acids as phosphorus analogues of naturally occurring amino carboxylic acids have received much interest due to their biological activity. Because of the tetrahedral structure of the phosphonic/inic moiety, they mimic tetrahedral intermediates of hydrolysed esters, amides and peptides. Thus, they often act as inhibitors for esterases, peptidases and related enzymes and metalloenzymes. Phosphono/phosphinopeptides containing P-terminal aminoalkylphosphonic/inic acid display bacteriostatic and herbicidal properties and promising antitumor activity [Pt(II) complexes]. As consequence, the acids and the derived peptides have been used in a medical treatment of some diseases.

       We are interested in chemistry of complexes of the acids and their peptides with both hard and soft metals. In comparision with the complexing properties of the common acids and their peptides, complexes of aminophosphonic acids are more stable (higher basicity of the phosphorus ligand) and also can exist as protonated complexes. On the other hand, coordination of several phosphonic groups to a metal ion results in less stable complexes (coloumbic repulsion of two negative charges on phosphonate anion). Phosphonic dipeptides show the same properties as the simple acids and differences in properties between their diastereoisomers are more pronounced then in case of common dipeptides (due to larger hydrophobic interections of side chains).

       In contrast to the common amino acids, complexes of aminophosphinic acids are less stable (lower basicity of the phosporus ligand) and their coordination ability depends on a substituent at phosphorus atom. Their dipeptides display toward Cu²⁺ ion unusual coordination mode with preference of bis(dipeptide)copper^(II) complexes.

Selected Publications:

P. Hermann, I. Lukes:
"Complexing Properties of Phosphonodipeptides Containing Aminomethylphosphonic Acid."
J. Chem. Soc., Dalton Trans. 1995, 2605-10.     > Abstract

P. Hermann, I. Lukes, P. Vojtisek, I. Cisarova:
"Complexing Properties of Phosphonodipeptides Containing 1-aminoethylphosphonic Acid."
J. Chem. Soc., Dalton Trans. 1995, 2611-18.     > Abstract

J. Rohovec, I. Lukes, P. Vojtisek, I. Cisarova, P. Hermann:
"Complexing Properties of Phosphinic Analogues of Glycine."
J. Chem. Soc., Dalton Trans. 1996, 2685-91.     > Abstract

L. Blaha, I. Lukes, J. Rohovec, P. Hermann:
"Complexes of Platinum(II) and Palladium(II) with Aminomethylphosphonic Acid and Glycylaminomethylphosphonic Acid."
J. Chem. Soc., Dalton Trans. 1997, 2621-8.     > Abstract , > PDF

I. Lukes, L. Blaha, F. Kesner, J. Rohovec, P. Hermann:
"Complexeing Properties of Diastereoisomers of 1-(L-Methionylamino)-ethylphosphonic Acid."
J. Chem. Soc., Dalton Trans. 1997, 2629-37.     > Abstract , > PDF

M. Lukáš, M. Kývala, P. Hermann, I. Lukeš, D. Sanna. G. Micera:
"Complexing properties of [(glycylamino)methyl]phosphinic acids towards Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ ions in aqueous solutions"
J. Chem. Soc., Dalton Trans. 2001, 2850-57     > DOI: 10.1039/b103357n

V. Kubíček, P. Vojtíšek, J. Rudovský, P. Hermann, I. Lukeš:
"Complexes of Divalent Transition Metal Ions with Bis(aminomethyl)phosphinic Acid in Aqueous Solution and in the Solid State"
J. Chem. Soc. – Dalton Trans., 2003, 3927–37     > DOI: 10.1039/b305844a