TY - JOUR
T1 - Synthesis, magnetic properties, and phosphoesterase activity of dinuclear cobalt(II) complexes
AU - Daumann, Lena J.
AU - Comba, Peter
AU - Larrabee, James A.
AU - Schenk, Gerhard
AU - Stranger, Robert
AU - Cavigliasso, German
AU - Gahan, Lawrence R.
PY - 2013/2/18
Y1 - 2013/2/18
N2 - A series of dinuclear cobalt(II) complexes has been prepared and characterized to generate functional and spectroscopic models for cobalt(II) substituted phosphoesterase enzymes such as the potential bioremediator GpdQ. Reaction of ligands based on 2,2'-(((2-hydroxy-5-methyl-1,3-phenylene) bis(methylene))bis((pyridin-2-ylmethyl)azanediyl)))diethanol (L1) and 2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)-4-methylphenol (L2) with cobalt(II) salts afforded [Co2(CO2EtH 2L1)(CH3COO)2](PF6), [Co 2(CO2EtL2)(CH3COO)2](PF 6), [Co2(CH3L2)(CH3COO) 2](PF6), [Co2(BrL2)(CH3COO) 2](PF6), and [Co2(NO2L2)(CH 3COO)2](PF6). Complexes of the L2 ligands contain a coordinated methyl-ether, whereas the L1 ligand contains a coordinated alcohol. The complexes were characterized using mass spectrometry, microanalysis, X-ray crystallography, UV-vis-NIR diffuse reflectance spectroscopy, IR absorption spectroscopy, solid state magnetic susceptibility measurements, and variable-temperature variable-field magnetic circular dichroism (VTVH MCD) spectroscopy. Susceptibility studies show that [Co 2(CO2EtH2L1)(CH3COO) 2](PF6), [Co2(CO2EtL2)(CH 3COO)2](PF6), and [Co2(CH 3L2)(CH3COO)2](PF6) are weakly antiferromagnetically coupled, whereas [Co2(BrL2)(CH 3COO)2](PF6) and [Co2(NO 2L2)(CH3COO)2](PF6) are weakly ferromagnetically coupled. The susceptibility results are confirmed by the VTVH MCD studies. Density functional theory calculations revealed that magnetic exchange coupling occurs mainly through the phenolic oxygen bridge. Implications of geometry and ligand design on the magnetic exchange coupling will be discussed. Functional studies of the complexes with the substrate bis(2,4-dinitrophenyl) phosphate showed them to be active towards hydrolysis of phosphoester substrates.
AB - A series of dinuclear cobalt(II) complexes has been prepared and characterized to generate functional and spectroscopic models for cobalt(II) substituted phosphoesterase enzymes such as the potential bioremediator GpdQ. Reaction of ligands based on 2,2'-(((2-hydroxy-5-methyl-1,3-phenylene) bis(methylene))bis((pyridin-2-ylmethyl)azanediyl)))diethanol (L1) and 2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)-4-methylphenol (L2) with cobalt(II) salts afforded [Co2(CO2EtH 2L1)(CH3COO)2](PF6), [Co 2(CO2EtL2)(CH3COO)2](PF 6), [Co2(CH3L2)(CH3COO) 2](PF6), [Co2(BrL2)(CH3COO) 2](PF6), and [Co2(NO2L2)(CH 3COO)2](PF6). Complexes of the L2 ligands contain a coordinated methyl-ether, whereas the L1 ligand contains a coordinated alcohol. The complexes were characterized using mass spectrometry, microanalysis, X-ray crystallography, UV-vis-NIR diffuse reflectance spectroscopy, IR absorption spectroscopy, solid state magnetic susceptibility measurements, and variable-temperature variable-field magnetic circular dichroism (VTVH MCD) spectroscopy. Susceptibility studies show that [Co 2(CO2EtH2L1)(CH3COO) 2](PF6), [Co2(CO2EtL2)(CH 3COO)2](PF6), and [Co2(CH 3L2)(CH3COO)2](PF6) are weakly antiferromagnetically coupled, whereas [Co2(BrL2)(CH 3COO)2](PF6) and [Co2(NO 2L2)(CH3COO)2](PF6) are weakly ferromagnetically coupled. The susceptibility results are confirmed by the VTVH MCD studies. Density functional theory calculations revealed that magnetic exchange coupling occurs mainly through the phenolic oxygen bridge. Implications of geometry and ligand design on the magnetic exchange coupling will be discussed. Functional studies of the complexes with the substrate bis(2,4-dinitrophenyl) phosphate showed them to be active towards hydrolysis of phosphoester substrates.
UR - http://www.scopus.com/inward/record.url?scp=84874026429&partnerID=8YFLogxK
U2 - 10.1021/ic302418x
DO - 10.1021/ic302418x
M3 - Article
SN - 0020-1669
VL - 52
SP - 2029
EP - 2043
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 4
ER -