The N4O3 coordinating heptadentate imidazolidinyl phenolate ligand, H3L (2-(20-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine) forms with Cu(II) a rare aqua bridged complex [{Cu2(l-L)(l-H2O)}2](ClO4)2 . 4.5H2O(1 .4.5H2O). Complex 1 . 4.5H2O contains two crystallo- graphically different but chemically equivalent dinuclear [Cu2(l-L)(l-H2O)]+cationic units in the asymmetric unit. The copper atoms of each dinuclear unit are in a distorted square-pyramidal environmentand are held together by phenolate, imidazolidinyl and aqua bridges with a Cu...Cu separation of av.3.34 Å. The compound exhibits a very weak antiferromagnetic exchange interaction (J = -0.77 cm-1, H ˆ = -2 JS1Sˆ2) between the two copper(II) (S = 1/2) ions. The 1H NMR spectrum of the complex shows a total of 17 hyperfine shifted peaks, as expected from the idealized Cs symmetry of the compound, spread over a very large window of chemical shift, spanning about 250 ppm. The complex, having an appropriate intermetallic separation for catechol binding, shows catecholase like activity in MeCN at 25 °C, with the aerobic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butylquinone (3,5-DTBQ).
Aqua bridged Cu2 dimer of a heptadentate N4O3 coordinating ligand: Synthesis, structure and magnetic properties
BERTOLASI, Valerio;
2009
Abstract
The N4O3 coordinating heptadentate imidazolidinyl phenolate ligand, H3L (2-(20-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine) forms with Cu(II) a rare aqua bridged complex [{Cu2(l-L)(l-H2O)}2](ClO4)2 . 4.5H2O(1 .4.5H2O). Complex 1 . 4.5H2O contains two crystallo- graphically different but chemically equivalent dinuclear [Cu2(l-L)(l-H2O)]+cationic units in the asymmetric unit. The copper atoms of each dinuclear unit are in a distorted square-pyramidal environmentand are held together by phenolate, imidazolidinyl and aqua bridges with a Cu...Cu separation of av.3.34 Å. The compound exhibits a very weak antiferromagnetic exchange interaction (J = -0.77 cm-1, H ˆ = -2 JS1Sˆ2) between the two copper(II) (S = 1/2) ions. The 1H NMR spectrum of the complex shows a total of 17 hyperfine shifted peaks, as expected from the idealized Cs symmetry of the compound, spread over a very large window of chemical shift, spanning about 250 ppm. The complex, having an appropriate intermetallic separation for catechol binding, shows catecholase like activity in MeCN at 25 °C, with the aerobic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butylquinone (3,5-DTBQ).I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
