A new extended metal-organic framework [Cu(H2btec)(bipy)]∞ (1) (H4btec= 1,2,4,5-benzenetetracarboxylic acid; bipy= 2,2′-bipyridine) has been hydrothermally synthesized. Violet crystals are formed in a monoclinic system with a space group C2/c; a = 10.1810(18) Å, b = 14.4360(18) Å, c= 12.894(3) Å, β= 112.94(3)°. In the title compound 1 each Cu(II) centre has a distorted square planar environment, completed by two N atoms from one bipy ligand and two O atoms belonging to two dihydrogen benzene-1,2,4,5-tetracarboxylate anions (H2btec2−). The {Cu(bipy)}2+ moieties are bridged by H2btec2− anions to form an infinite one-dimensional coordination polymer with a zig-zag chain structure along the c axis. A double-chain structure is formed by hydrogen bonds between adjacent zig-zag chains. There are also π–π stacking interactions between the bipy ligands, with an average distance of 3.62 Å resulting in a two-dimensional network structure. Compound 1 was tested as a catalyst for the oxidation of cyclohexene and styrene, with tert-butyl hydroperoxide (TBHP) as oxidant. The catalytic activity (24 h and 75 °C) found for [Cu(H2btec)(bipy)]∞ shows a high value for the conversion of cyclohexene (64.5%), and a lower one for styrene (23.7%). High turnover frequency (TOF) values for the epoxide products were observed, indicating that the catalyst synthesized in this work, not only has a high activity and selectivity for epoxidation reactions but is also very efficient.
The metal–organic framework [Cu 2 (bipy) 2 (btec)] ∞ was used as a heterogeneous catalyst in the liquid phase oxidation of styrene and cyclohexene with tert -butylhydroperoxide (TBHP) as the oxidant either in water–dichloroethane or n -decane medium.
The synthesis and catalytic activity of a novel heteronuclear CuIIand LaIIImetal organic framework (MOF) having pyridinedicarboxylic acid (CuLa-MOF) is reported.
The copper (II) complexes (CuL2) were prepared by reaction of with the corresponding derivatives of acylthioureas in a Cu:HL molar ratio of 1:2. Acylthiourea ligands, N,N‐diethyl‐N′‐(R‐benzoyl) thiourea (HL1-3) [R=H, o‐Cl and p‐NO2] were synthesized in high yield (78‐83%) and characterized by elemental analysis, infrared spectroscopy, 1H and 13C NMR spectroscopy. The complexes CuL2 were characterized by elemental analysis, IR, FAB(+)‐MS, magnetic susceptibility measurements, EPR and cyclic voltammetry. The crystal structure of the complex Cu(L2)2 shows a nearly square‐planar geometry with two deprotonated ligands (L) coordinated to CuII through the oxygen and sulfur atoms in a cis arrangement. The antitumor activity of the copper(II) complexes with acylthiourea ligands was evaluated in vitro against the mouse mammary adenocarcinoma TA3 cell line. These complexes exhibited much higher cytotoxic activity (IC50 values in the range of 3.9‐6.9 μM) than their corresponding ligands (40‐240 μM), which indicates that the coordination of the chelate ligands around the CuII enhances the antitumor activity and, furthermore, this result confirmed that the participation of the nitro and chloro substituent groups in the complex activities is slightly relevant. The high accumulation of the complexes Cu(L2)2 and Cu(L3)2 in TA3 tumor cells and the much faster binding to cellular DNA than Cu(L1)2 are consistent with the in vitro cytotoxic activities found for these copper complexes.
1 January 2003 in Bioinorganic Chemistry and Applications
A low-molecular weight chromium-containing fraction of the material resulting from dichromate reduction by bovine liver homogenate was investigated by NMR and ES-MS. The ES-MS spectrum showed a readily detectable peak at m/z 786.1. The same molecular weight reasonably agreed with the relatively low diffusion coefficient measured by NMR-DOSY experiments on the main species observed in the (1)H NMR spectrum. At least two downfield shifted and broad paramagnetic signals were apparent in the (1)H NMR spectrum. Temperature dependence of chemical shift was exploited in order to estimate the diamagnetic shift of the signals in the diamagnetic region of the spectrum. 2D TOCSY, NOESY, COSY and (1)H-(13)C HMQC spectra revealed the presence of aromatic protons (which were assigned as His residues), Gly and some other short chain amino-acids. Combinations of the molecular masses of such components together with acetate (which is present in the solution) and chromium atoms allowed a tentative proposal of a model for the compound.