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Metal Complexes of 4,11‐Dimethyl‐1,4,8,11‐tetraazacyclotetradecane‐1,8‐bis(methylphosphonic acid) – Thermodynamic and Formation/Decomplexation Kinetic Studies
Author(s) -
Svobodová Ivona,
Havlíčková Jana,
Plutnar Jan,
Lubal Přemysl,
Kotek Jan,
Hermann Petr
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900358
Subject(s) - chemistry , ligand (biochemistry) , cyclam , protonation , copper , trigonal bipyramidal molecular geometry , metal , square pyramidal molecular geometry , inorganic chemistry , yield (engineering) , medicinal chemistry , crystallography , stereochemistry , polymer chemistry , ion , crystal structure , organic chemistry , biochemistry , materials science , receptor , metallurgy
The macrocyclic ligand with two methylphosphonic acid pendant arms, 4,11‐dimethyl‐1,4,8,11‐tetraazacyclotetradecane‐1,8‐bis(methylphosphonic acid) (1,8‐H 4 Me2 te2p, H 4 L 3 ), was synthesized by a new simple approach. The product of the reaction of quarternized formaldehyde cyclam aminal with the sodium salt of diethyl phosphite was hydrolyzed to give a very high yield of the title ligand. The (H 6 L 3 ) 2+ cation in the solid state is protonated on all ring nitrogen atoms and on each phosphonate group. In the solid‐state structure of [Cu(H 3 L 3 )][Cu(H 2 L 3 )]PF 6 · 3H 2 O, neutral as well as positively charged complex species are present. Molecular structures of both species are very similar having the copper(II) ion in a coordination environment between square‐pyramidal and trigonal‐bipyramidal arrangements ( τ = 0.43 and 0.48) with one pendant arm non‐coordinated. The ligand forms stable complexes with transition‐metal ions showing a high selectivity for divalent copper atoms. The formation of complexes of the ligand with Cu II , Zn II and Cd II is fast, confirming the acceleration of complexation due to the presence of the strongly coordinating pendant arms. Acid‐assisted decomplexation is fast for all three metal ions. Therefore, the copper(II) complex is not suitable for medicinal applications employing copper radioisotopes, but the title ligand motive can be employed in copper(II) separation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)