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Construction of ZnII compounds with a chelating 2,2?-dipyridylamine (Hdpa) ligand: Anion effect and catalytic activities

The structures of new compounds containing ZnII ions and Hdpa (2,2?-dipyridylamine)-chelating ligands were determined. The Hdpa chelating ligands coordinate to ZnII ions to form mononuclear units (1 and 5), and intermolecular non-classical hydrogen-bond (C-H…O or N/C-H…I) interactions generate polymeric compounds. The chelating ligands with a bipyridyl moiety form mostly mononuclear complexes of different types (I, II and III), and the combination of this ligand with a sulfate anion can produce polymeric species (Type IV). Interestingly, homogeneous catalyst 1 catalyzed efficiently the transesterification of a variety of esters with different alcohols, and hydrogen-bonded polymer 5 showed the heterogeneous catalytic activity for the transesterification reactions. Preliminary selectivity test of primary over secondary alcohol protection in the presence of 1 provided, exclusively, the primary acetate, which suggests the potential utility of this catalyst to be selective for primary alcohols. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

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Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

A new application about (2R,3S,4R,5R)-2,3,4,5-Tetrahydroxy-6-(((2S,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yl)oxy)hexanal

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Cadmium(II) complexes of 5-bromo-salicylaldehyde and alpha-diimines: Synthesis, structure and interaction with calf-thymus DNA and albumins

Five Cd(II) complexes, four dinuclear (1-4) and a mononuclear one (5), with the anion of 5-Br-salicylaldehyde (5-Br-salo-), were synthesized and characterized as [Cd(5-Br-salo)2(CH3OH)]2 (1), [Cd(5-Br-salo)2(bipy)]2 (2), [Cd(5-Br-salo)2(phen)]2 (3), [Cd(5-Br-salo)(neoc)(NO3)]2 (4) and [Cd(5-Br-salo)2(dpamH)] (5). The complexes were characterized by spectroscopy (IR, UV-vis, 1H NMR), elemental analysis and molar conductivity measurements. The structures for three complexes (2, 3 and 5) were determined by X-ray crystallography providing different coordination modes of the 5-Br-salicylaldehydo ligand. The complexes bind to DNA mainly by intercalation, as concluded by the viscosity measurements and the EB-displacement studies from the EB-DNA complex and present high DNA-binding constants (Kb), as calculated by the Wolfe-Shimer equation and plots. The interaction of the complexes with serum albumins was studied by fluorescence emission spectroscopy and the determined binding constants exhibit relative high values.

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Molecular Structure, Acidic Properties, and Kinetic Behavior of the Cationic Complex (Methyl)(dimethyl sulfoxide)(bis-2-pyridylamine)platinum(II) Ion

The complex [PtMe(dpa) (Me2SO)]+(CF3SO3)- (dpa = bis(2-pyridyl)amine) crystallizes in the monoclinic space group P21/c with a = 11.010(2) A, b = 18.366(2) A, c = 10.333(5) A, beta= 111.62(2), and Z = 4. Least-squares refinement of the structure led to an R factor of 2.41%. To avoid steric repulsions, the chelate six-membered ring assumes a boat configuration in which the two pyridyl rings are folded with a dihedral angle of 46.4(1). There is a strong hydrogen-bonding interaction involving the amine hydrogen (N3) and a triflate anion oxygen O3, 2.898(5) A. The tendency by the NH group of the ligand moiety to attract anions is maintained in a solution of nonpolar solvents. Tight ion-pairs of structure similar to that in the solid state are formed with PF6-, BF4-, CF3SO3-, and Cl- in chloroform, as shown by the strong dependence of the chemical shifts of the NH, H(3), and H(3?) protons of the dpa ligand on the nature of the counterion. 19F{1H} HOESY experiments on [PtMe(dpa)(Me2SO)]+(PF6)- in CD2Cl2 confirmed that the preferential position of the counterion is close to the NH proton. The absorption spectra are also strongly affected by the nature of the counterion. This allowed for a stopped-flow measure of the PF6- for Cl- exchange rate at the NH site, which is a bimolecular process with k2 = 96.4 ¡À4 M-1 s-1. The cation [PtMe(dpa)(Me2SO)]+ shows acidic properties in water (pKcan be isolated on basification. Ion-pairing and full deprotonation of the amine ligand have remarkably little effect on the reactivity, as shown by the comparison of the rates of isotopic exchange of dimethyl sulfoxide of these species followed by 1H NMR in chloroform. The rates of substitution of dimethyl sulfoxide from by various charged nucleophiles were measured in methanol, where ion-pairing effects are absent, and compared with those of the parent (phen = 1,10-phenanthroline) complex. Because of the reduced capacity of electron withdrawal from the metal of the ancillary ligand, the dpa complex is less reactive and possesses a minor nucleophilic discrimination ability compared with the phen complex.

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Synthesis, structures, electrochemistry and magnetic properties of a cyano-bridged {Fe2Co2} molecular square

The reaction of tricyanometallate precursor, (Bu4N)[(Tp*) Fe(CN)3] (Tp* = hydrotris(3,5-dimethylpyrazol-l-yl)borate) with Co(ClO4)2¡¤6H2O in the presence of the bidentate dpa (dpa = 2,2?-dipyridyl amine) ligand affords one novel cyano-bridged heterobimetallic {Fe2Co2} molecular square, [FeIII(Tp*)(CN)3]2[CoII(dpa) 2]2?2ClO4?4H2O? 4CH3OH (1). The molecular structure was determined by single-crystal X-ray diffraction. In compound 1, FeIII ion is coordinated by three cyanide carbon atoms and three nitrogen atoms of Tp* anions. Whereas, the CoII ion is surrounded by two cyanide nitrogen atoms and four nitrogen atoms from two bidentate dpa ligands. Cyclic voltammetry (CV) measurements showed that complex 1 exhibited one quasi-reversible waves (0.1 V vs SCE) in the reduction process, and irreversible waves in the oxidation process. Magnetic measurements indicate that complex 1 exhibits a strong intramolecular ferromagnetic interaction between the low-spin FeIII(S = 1/2) and high-spin CoII(S = 3/2) ions.

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The preparation and crystal structures of Cu(Hdpa)(chp)2 and a new phaseof Cu(dpa)2 [Hdpa=2-(pyridyl-2-amino)-pyridine, Hchp=6-chloro-2-hydroxy pyridine]

The synthesis and crystal structure of Cu(Hdpa)(chp)2 (I) are reported. The copper environment is six coordinate with Hdpa and one of the chp ligands bonding in a chelating fashion. The second pyridine is bound through N, the O atom takes up the sixth coordination site but is also hydrogen bonded to the Hdpa ligand of a second Cu(Hdpa)(chp)2 unit, forming a centrosymmetric dimer. A new (orthorhombic) phase of Cu(dpa)2 (II) has also been found, in which distorted tetrahedral copper(II) complexes are linked through a network of H bonds between the deprotonated dpa ligand and C-H bonds meta- to the pyridyl nitrogen donor.

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Tetrahydropyran – Wikipedia,
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Remarkable effects of axial pi* coordination on the Cr-Cr quadruple bond in dichromium paddlewheel complexes

It is well-known that donation of electron density into the sigma* orbital of a Cr-Cr quadruple bond causes major lengthening of the Cr-Cr distance, and there is some prior evidence that a similar lengthening is caused by dative interaction with the pi* orbitals. Some molecules have now been made that allow a definitive assessment of this axial pi* effect. A molecule has been designed to ensure that there is axial donation into the pi* orbitals but not onto the sigma* orbital; ligands have been used in which the donor atoms are tethered to the bridging ligands in such a way that they can reach only the pi* orbitals but not the sigma* orbital. The ligands used for this purpose are the anions of 2,6-di(phenylimino)piperidine (DPhIP) and 2,2?-dipyridylamine (dpa). In the compound Cr2(DPhIP)4 four imino nitrogen lone pairs are suitably positioned to donate to the pi* orbitals and the Cr-Cr bond length is 2.265(1) A. For direct comparison, the compound Cr2(PhIP)4 (PhIP is the anion of 2-(phenylimino)piperidine) was made and found to have a Cr-Cr distance of 1.858(1) A. In this case the ligand is very similar to DPhIP except that it has no donor nitrogen atoms available for axial pi* donation. Thus, the cumulative effect of donation from four nitrogen atoms is very large, namely, 0.4 A in the Cr-Cr distance. The Cr2(dpa)4 molecule occurs in three different crystalline compounds, in all of which there are slightly different conformations, but the same Cr-Cr distance, 1.94 ¡À 0.01 A; these may be compared to that in the compound Cr2(mpa)4 (1.87 A) in which the bridging is quite similar but there are no tethered additional donor atoms.

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Nonhelical heterometallic [Mo2M(npo)4(NCS)2] string complexes (M = Fe, Co, Ni) with high single-molecule conductance

Using the planar 1,8-naphthyridin-2(1H)-one (Hnpo) ligand, novel nonhelical HMSCs [Mo2M(npo)4(NCS)2] (M = Fe, Co, Ni) were synthesised and they exhibited high single-molecule conductance.

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Structure, DNA/proteins binding, docking and cytotoxicity studies of copper(II) complexes with the first quinolone drug nalidixic acid and 2,2??dipyridylamine

This work presents the synthesis, structural characterization and biological affinity of the newly synthesized copper(II) complexes with the first antibacterial quinolone drug nalidixic acid (nal) or N?donor ligand 2,2??dipyridylamine (bipyam). [Cu(II)(nal)(bipyam)Cl], (2) reveals a distorted square pyramidal based geometry in Cu(II) atom confirmed by X-ray crystallography technique. The theoretical stabilities and optimized structures of the complex were obtained from DFT calculations. The ability of the complexes to bind with calf thymus DNA (CT DNA) were investigated by electronic absorption, fluorescence, circular dichroism, and viscosity measurements techniques. The experimental results reveal that the complexes strongly interact with CT DNA via intercalative mode but complex 2 exhibits the highest affinity giving Kb = 3.91 ¡À 0.13 ¡Á 106, M?1. The fluorescence spectroscopy measurements show that both complexes have the superior ability to the replacement of EtBr from DNA-bound EtBr solution and bind to DNA through intercalative mode. Both complex also shows the superior affinity towards proteins with comparatively high binding constant values which have been further revealed by fluorescence spectroscopy measurements. Molecular docking analysis indicates that the interaction of the complexes and proteins are stabilized by hydrogen bonding and hydrophobic interaction. Furthermore, the results of in vitro cytotoxicity reveal that the complex 2 has excellent cytotoxicity than 1 against human breast cancer cell lines (MCF-7).

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Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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Synthesis and coordination chemistry of 2-(Di-2-pyridylamino)pyrimidine; Structural aspects of spin crossover in an FeII complex

2-(Di-2-pyridylamino)pyrimidine (L), a potentially ditopic tetradentate ligand, was synthesized from commercially available di-2-pyridylamine and 2-chloropyrimidine. Despite being capable of bridging two metal atoms with bidentate chelation of both metal centres, L prefers to chelate or bridge through the more basic pyridyl donors of the di-2-pyridylamine moiety. Mononuclear trans-[Fe(NCS)2(L)2] and [Cu(L) 2(H2O)](BF4)2¡¤H2O complexes, and a discrete [Ag2(L)4](PF6) 2 metallo-macrocycle, were isolated and structurally characterized by X-ray crystallography. A mononuclear palladium complex [PdCl 2(L)]¡¤(solvate), where solvate=1/2H2O or CH2Cl2, was also readily obtained in 71% yield. One example of the ligand acting as a bis(bidentate) bridging ligand was observed in a dinuclear [(PdCl2)2(L)]¡¤3/4H2O complex that was obtained only in very low yield (?3%) from the reaction that produced [PdCl2(L)]¡¤1/2H2O. trans-[Fe(NCS)2(L)2] undergoes a temperature-dependent high-spinlow-spin crossover at ?205K that was observed by X-ray crystallography and magnetic measurements, and attempts were made to understand the structural basis of this process. Despite efforts to isolate examples of L bridging two iron(ii) centres, only the mononuclear trans-[Fe(NCS) 2(L)2] species could be obtained.

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Luminescence and electroluminescence of Al(III), B(III), Be(II) and Zn(II) complexes with nitrogen donors

Blue luminescent complexes of aluminum(III), boron(III), beryllium(II) and zinc(II) using ligands that contain only nitrogen donor atoms are presented. The ligands in these complexes are based on di-2-pyridylamine and 7-azaindole. Complexes containing derivatives of 7-azaindole and di-2-pyridylamine are described. Electroluminescent properties for some of the promising compounds are also discussed.

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