Structural correlation of catecholase-like activities of oxy-bridged dinuclear copper(II) complexes.
Eight oxy-bridged dinuclear copper(II) complexes with catecholase-like sites, [Cu(L1)X]2 (HL1 = 1-diethylaminopropan-2-ol, X=N3- 1, NCO- 2, and NO2- 3), [Cu(L2)X]2 (HL2=N-ethylsalicylaldimine, X=NO3- 4, Cl- 5, N3- 6, NCS- 7), and [Cu(L3)]2(ClO4)2, 8 (HL3=N-(salicylidene)-N'-(2-pyridylaldene)propanediamine) have been prepared and characterized. The single crystal X-ray analysis show that the structures of complexes 6 and 8 are dimeric with two adjacent copper(II) atoms bridged by pairs of micro-oxy atoms from the L2 and L3 ligands. Magnetic susceptibility measurements in the temperature range 4-300 K indicate significant antiferromagnetic coupling for 4, 5 and 7 and ferromagnetic coupling for 6 between the copper(II) atoms. The catecholase activity of complexes for the oxidation of 3,5-di-tert-butylcatechol by O2 was studied and it was found that the complexes with the bond distance of Cu(II)...Cu(II) located at 2.9-3.0 A show higher catecholase activity.
Kao
C H
CH
Department of Chemistry, Tamkang University, Tamsui, Taiwan.
Wei
H H
HH
Liu
Y H
YH
Lee
G H
GH
Wang
Y
Y
Lee
C J
CJ
D020134:Catalytic Domain; D004156:Catechol Oxidase / Q000737:chemistry*; D002396:Catechols / Q000378:metabolism; D003300:Copper; D018360:Crystallography, X-Ray; D007700:Kinetics; D008024:Ligands; D008280:Magnetics; D018716:Molecular Mimicry; D009942:Organometallic Compounds / Q000737:chemistry* / Q000378:metabolism*; D010084:Oxidation-Reduction; D010100:Oxygen; D013329:Structure-Activity Relationship
D002396:Catechols; D008024:Ligands; D009942:Organometallic Compounds; C054068:3,5-di-tert-butylcatechol; D003300:Copper; D004156:Catechol Oxidase; D010100:Oxygen