3099-30-7Relevant articles and documents
Copper(ii) complexes based on tripodal pyridyl amine derivatives as efficient anticancer agents
Massoud, Salah S.,Louka, Febee R.,Tusa, Ada F.,Bordelon, Nicole E.,Fischer, Roland C.,Mautner, Franz A.,Van?o, Ján,Ho?ek, Jan,Dvo?ák, Zdeněk,Trávní?ek, Zdeněk
, p. 6186 - 6196 (2019)
The complexes [Cu(TPA)Cl]ClO4·?H2O (1-ClO4), [Cu(6-MeTPA)Cl]ClO4/PF6 (2-ClO4/2-PF6), [Cu(6-Me2TPA)Cl]PF6 (3-PF6), [Cu(BPQA)Cl]ClO4/PF6 (4-ClO4/4-PF6), [Cu(BPQA)Cl]ClO4/PF6 (4-ClO4/4-PF6), [Cu(BQPA)Cl]ClO4/PF6 (5-ClO4/PF6), [Cu(L1)Cl]ClO4/PF6 (6-ClO4/6-PF6), [Cu(L2)Cl]ClO4 (7-ClO4) and [Cu(L3)Cl]ClO4 (8-ClO4) have been synthesized and structurally characterized by spectroscopic techniques and single X-ray crystallography. The in vitro cytotoxicity of the prepared Cu(ii) complexes was evaluated against A2780 (ovarian), A2780R (cisplatin-resistant variant) and MCF7 (breast cancer) human cancer cell lines. Overall, the complexes revealed significant-to-moderate cytotoxicity, with the best results obtained for the complexes [Cu(BQPA)Cl]ClO4 (5-ClO4) and [Cu(BQPA)Cl]PF6 (5-PF6), showing IC50 values within the range of 4.7-10.8 μM. The ability of the most cytotoxic complexes to cleave DNA under different conditions and the mechanisms underlying this activity were assessed by means of agarose gel electrophoresis.
Interplay Between Steric and Electronic Effects: A Joint Spectroscopy and Computational Study of Nonheme Iron(IV)-Oxo Complexes
Mukherjee, Gourab,Alili, Aligulu,Barman, Prasenjit,Kumar, Devesh,Sastri, Chivukula V.,de Visser, Sam P.
, p. 5086 - 5098 (2019/03/17)
Iron is an essential element in nonheme enzymes that plays a crucial role in many vital oxidative transformations and metabolic reactions in the human body. Many of those reactions are regio- and stereospecific and it is believed that the selectivity is guided by second-coordination sphere effects in the protein. Here, results are shown of a few engineered biomimetic ligand frameworks based on the N4Py (N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) scaffold and the second-coordination sphere effects are studied. For the first time, selective substitutions in the ligand framework have been shown to tune the catalytic properties of the iron(IV)-oxo complexes by regulating the steric and electronic factors. In particular, a better positioning of the oxidant and substrate in the rate-determining transition state lowers the reaction barriers. Therefore, an optimum balance between steric and electronic factors mediates the ideal positioning of oxidant and substrate in the rate-determining transition state that affects the reactivity of high-valent reaction intermediates.
Facial triad modelling using ferrous pyridinyl prolinate complexes: Synthesis and catalytic applications
Moelands, Marcel A. H.,Schamhart, Daniel J.,Folkertsma, Emma,Lutz, Martin,Spek, Anthony L.,Klein Gebbink, Robertus J. M.
, p. 6769 - 6785 (2014/05/06)
A series of new chiral pyridinyl prolinate (RPyProR) ligands and their corresponding Fe(ii) triflate and chloride complexes are reported. The ligands possess an NN′O coordination motif, as found in the active site of non-heme iron enzymes with the so-called 2-His-1-carboxylate facial triad. The coordination behaviour of these ligands towards iron turned out to be dependent on the counter ion (chloride or triflate), the crystallization conditions (coordinating or non-coordinating solvents) and the presence of substituents on the ligand. In combination with Fe(ii)(OTf)2, coordinatively saturated complexes of the type [Fe(L)2](OTf)2 are formed, in which the ligands adopt a meridional coordination mode. The use of FeCl 2 in a non-coordinating solvent leads to 5-coordinated complexes [Fe(L)(Cl)2] with a meridional N,N′,O ligand. Crystallization of these complexes from a coordinating solvent leads to 6-coordinated [Fe(L)(solv)(Cl)2] complexes (solv = methanol or acetonitrile), in which the N,N′,O ligand is coordinated in a facial manner. For RPyProR ligands bearing a 6-Me substituent on the pyridine ring, solvent coordination and, accordingly, ligand rearrangement are prevented by steric constraints. The complexes were tested as oxidation catalysts in the epoxidation of alkene substrates in acetonitrile with hydrogen peroxide as the oxidant under oxidant limiting conditions. The complexes were shown to be especially active in the epoxidation of styrene type substrates (styrene and trans-beta-methylstyrene). In the best case, complex [Fe(6-Me-PyProNH2)Cl2] (15) allowed for 65% productive consumption of hydrogen peroxide toward epoxide and benzaldehyde products. This journal is the Partner Organisations 2014.
