Alkaline earth metal ions mediated self-assembly in the presence of 1,10-phenanthroline, nitrate and tetrafluoroborate anions

1,10-Phenanthroline (phen) was reacted with various combinations of two and in one of the cases with three alkaline earth metal cations taken in equimolar ratio. In all the competitive reactions it was obtained only one product free of any impurities, which is in accordance with the theory of self-assembly processes. The compound [Ca(phen)2(H2O)2(NO3)]NO3 was synthesized in all the reactions where Ca(2+) was involved. In contrast, none of the reactions led to the preparation of a strontium complex. Two of the reactions, in which participated Be(2+), resulted in the compound (phen)3(H+)2(NO(-)(3))2. The second group of competitive reactions was carried out with 1,10-phenanthroline and a given alkaline earth metal cation in the presence of the anions NO(3)(-) and BF(4)(-). These led to the compounds Mg(phen)4(BF4)2(H2O)3, [Ca(phen)2(H2O)2(NO3)]BF4, Sr(phen)4(OH)(BF4)(H2O) and Ba(phen)3.5(BF4)2(H2O). All the newly synthesized substances were characterized by elemental analysis, IR- and FAB-mass-spectra.     

XPS studies on the host-guest interaction of 2,2′-Bipyridyl, 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline intercalated inα-zirconium phosphate

The host-guest interactions of 2,2-bipyridyl, 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline intercalated between the layers of crystalline-zirconium monohydrogen phosphate have been studied by X-ray photoelectron spectroscopy. Evidence that, on average, only one of the two nitrogen atoms of each aromatic diamine is protonated by the P-OH groups of the host is given. The acid-base interaction is strongly reduced on dehydration of the materials. The role of the cointercalated water is discussed, together with the probable disposition of the guests within the interlayer region.     

Formation of hydroxamic acids promoted by metal ions. interaction of aldehyde carbonyl group with C-nitroso group in the presence of ferric ions

Formation of N-phenyl substituted hydroxamic acids in the reaction of formaldehyde with substituted mtrosobenzene is strongly catalysed by Fe³⁺ ions, which stabilize the transition state for the rate-controlling proton transfer from the carbon of nitrosocarbinolic cation intermediate leading to the product, hydroxamic acid     

Structural diversity and supramolecular aggregation in calcium, strontium, and barium salicylates incorporating 1,10-phenanthroline and 4,4'-bipyridine: probing the softer side of group 2 metal ions with pyridinic ligands

Group 2 metal complexes [Ca(SA)2(phen)]n (1), [Sr2(SA)4(phen)4] (2), and [Ba(SA)2(phen)2]n (3) (SA = salicylate) have been obtained by the addition of 1,10-phenanthroline (phen) to the corresponding metal salicylates, while the bipyridine derivatives {[Ca3(SA)6(H2O)4](4bpy)2}n (4), {[Sr(SA)2(H2O)3](4bpy)1.5(H2O)}n (5), and {[Ba(SA)2(H2O)3]-(4bpy)1.5(H2O)}n (6) have been synthesized starting from the respective metal carbonates, salicylic acid (SA-H), and 4,4'-bipyridine (4bpy). The new compounds have been characterized by elemental analysis, pH measurements, thermal analysis, and spectroscopic measurements (IR, NMR, ultraviolet, and fluorescence). Molecular structure determination by single-crystal X-ray diffraction has been carried out for all the compounds. The thermal analysis studies indicate the loss of coordinated and/or lattice water molecules below 200 degrees C in 4-6 and the absence of any coordinated or uncoordinated water molecules in compounds 1-3. Compounds 1 and 3-6 exist as one-dimensional polymers while compound 2 crystallizes as a discrete dimer. Considerable variations have been observed in the molecular structures of 1-6 in terms of the geometry around the metal, the binding mode of salicylate, and the coordination behavior of the pyridine ligand. Calcium ion is hexacoordinated in 1, while in 4 both hexa- and heptacoordinated calcium ions are simultaneously present. Strontium exhibits coordination numbers of nine and eight in 2 and 5, respectively. The barium ions in 3 and 6 assume coordination numbers of eight and seven, respectively. While the OH group of the salicylate ligand does not directly bind the metal in 1-3, it coordinates to the metal ions in complexes in 4-6 in the un-ionized form. The 4bpy molecules show no direct ligation to the metal in 4-6; the phen ligands in 1-3, however, occupy one side of the coordination sphere around the metal. The presence of additional O-H...O, C-H...O, and N-H...O hydrogen bonding and pi-pi stacking in these compounds results in the formation of polymeric structures. The results obtained for the calcium complexes in this study have been compared with the available data in structural calcium chemistry with the aid of a detailed analysis of the Cambridge Structural Database.     

Ruthenium-cluster-mediated activation of all bonds of a methyl group of 6,6'-dimethyl-2,2'-bipyridine and 2,9-dimethyl-1,10-phenanthroline: transformation of the latter into a 2-alkenyl-9-methyl-1,10-phenanthroline ligand

The treatment of [Ru3(CO)12] with 6,6'-dimethyl-2,2'-bipyridine (Me2bipy) or 2,9-dimethyl-1,10-phenanthroline (Me2phen) in THF at reflux temperature gives the trinuclear dihydride complexes [Ru3(mu-H)2(mu3-L1)(CO)8] (L1 = HCbipyMe 1 a, HCphenMe 1 b), which result from the activation of two C-H bonds of a methyl group. The hexa-, hepta-, and pentanuclear derivatives [Ru6(mu3-H)(mu5-L2)(mu-CO)3(CO)13] (L2 = CbipyMe 2 a, CphenMe 2 b), [Ru7(mu3-H)(mu5-L2)(mu-CO)2(CO)16] (L2 = CbipyMe 3 a, CphenMe 3 b), and [Ru5(mu-H)(mu5-C)(mu-L3)(CO)13] (L3 = bipyMe 4 a, phenMe 4 b) can also be obtained by treating 1 a and 1 b with [Ru3(CO)12]. Compounds 2 a and 2 b have a basal edge-bridged square-pyramidal metallic skeleton with a carbyne-type C atom capping the four Ru atoms of the pyramid base. The structures of 3 a and 3 b are similar to those of 2 a and 2 b, respectively, but an additional Ru atom now caps a triangular face of the square-pyramidal fragment of the metallic skeleton. The most interesting feature of 2 a, 2 b, 3 a, and 3 b is that their carbyne-type C atoms were originally bound to three hydrogen atoms in Me2bipy or Me2phen and, therefore, they arise from the unprecedented activation of all three C-H bonds of C-bound methyl groups. The pentanuclear compounds 4 a and 4 b contain a carbide ligand surrounded by five Ru atoms in a distorted trigonal-bipyramidal environment. They are the products of a series of processes that includes the activation of all bonds (three C-H and one C-C) of organic methyl groups, and are the first examples of complexes having carbide ligands that arise from C-bonded methyl groups. The alkenyl derivatives [Ru5(mu5-C)(mu-p-MeC6H4CHCHphenMe)(CO)13] (5 b), [Ru5(mu-H)(mu5-C)(mu-p-MeC6H4CHCHphenMe)(p-tolC2)(CO)12] (6 b), and [Ru5(mu-H)(mu5-C)(mu-PhCHCHphenMe)(PhC2)(CO)12] (7 b) have been obtained by treating 4 b with p-tolyl- and phenylacetylene, respectively. Their heterocyclic ligands contain an alkenyl fragment in the position that was originally occupied by a methyl group. Therefore, these complexes are the result of the formal substitution of an alkenyl group for a methyl group of 2,9-dimethyl-1,10- phenanthroline.     

tert-Butoxide-mediated arylation of benzene with aryl halides in the presence of a catalytic 1,10-phenanthroline derivative

Sodium tert-butoxide mediates the coupling of aryl halides with benzene derivatives without the aid of transition metal catalysts but with a catalytic 1,10-phenanthroline derivative.     

A novel ditopic receptor and reversal of anion binding selectivity in the presence and absence of bound cation

A calix[4]arene-derived ditopic receptor 1 has been synthesized. In the absence of Na+, the receptor binds acetate in preference to diphenyl phosphate (as the tetrabutylammonium salts), but in the presence of Na+, the selectivity is reversed and the receptor, instead, binds diphenyl phosphate, and not acetate, which preferentially forms a salt ion-pair in free solution. [structure: see text]     

Scanning electrochemical microscopy. 51. Studies of self-assembled monolayers of DNA in the absence and presence of metal ions

Scanning electrochemical microscopy was used to examine electron transfer across a self-assembled monolayer of thiol-modified DNA duplexes on a gold electrode. The apparent rate constant for heterogeneous ET from a solution redox probe, Fe(CN)6(3-/4-), to the gold surface through ds-DNA was 4.6 (+/-0.2) x 10(-7) cm/s. With the addition of Zn2+, which resulted in the formation of a metalated DNA (M-DNA) monolayer, the rate constant increased to 5.0 (+/-0.3) x 10(-6) cm/s. Upon treating M-DNA with EDTA, the zinc ions were released from the monolayer and the original rate constant for the DNA duplexes was restored. The enhanced ET rate was also observed at a DNA monolayer treated with Ca2+ or Mg2+, which does not complex by the DNA bases to form M-DNA. The binding of these cations facilitated the monolayer penetration by the probe mediator Fe(CN)6(3-/4-) and accordingly caused an increased redox signal of the mediator at the ds-DNA-modified electrode. Cationic or neutral mediators were not blocked by the ds-DNA monolayer. These results suggest that although the increased electron transport through M-DNA could partially be ascribed to the intrinsic enhancement of electric conductivity of M-DNA, which has been confirmed by photochemical studies, the change in the surface charge of DNA monolayers on the electrode caused by the binding of metal ions to DNA molecules may play a more important role in the enhancement of current with M-DNA.     

A promising green method in cyclization reaction.Oxidation of 3-methylcatechol in the presence of 1,10-phenanthroline

Electrochemical oxidation of 3-methylcatechol as a model compound has been studied in the presence of 1,10-phenanthroline as a bi-dentate nucleophile in water/acetonitrile(70/30,v/v) solution using cyclic voltammetry and controlled-potential coulometry. The results revealed that anodically generated 3-methylcyclohexa-3,5-diene-1,2-dione participates in inter and intramolecular Michael addition reactions with 1,10-phenanthroline and via an ECEC pathway converts to the corresponding heterocyclic compound.The present work has led to the development of a facile and one-pot method with high atom economy under ambient conditions and in an undivided cell using a carbon electrode.     

Investigation of the binding of Salvianolic acid B to human serum albumin and the effect of metal ions on the binding

The studies on the interaction between HSA and drugs have been an interesting research field in life science, chemistry and clinical medicine. There are also many metal ions present in blood plasma, thus the research about the effect of metal ions on the interaction between drugs and plasma proteins is crucial. In this study, the interaction of Salvianolic acid B (Sal B) with human serum albumin (HSA) was investigated by the steady-state, synchronous fluorescence and circular dichroism (CD) spectroscopies. The results showed that Sal B had a strong ability to quench the intrinsic fluorescence of HSA through a static quenching mechanism. Binding parameters calculated showed that Sal B was bound to HSA with the binding affinities of 10(5) L mol(-1). The thermodynamic parameters studies revealed that the binding was characterized by positive enthalpy and positive entropy changes, and hydrophobic interactions were the predominant intermolecular forces to stabilize the complex. The specific binding distance r (2.93 nm) between donor (HSA) and acceptor (Sal B) was obtained according to F?rster non-radiative resonance energy transfer theory. The synchronous fluorescence experiment revealed that Sal B cannot lead to the microenvironmental changes around the Tyr and Trp residues of HSA, and the binding site of Sal B on HSA is located in hydrophobic cavity of subdomain IIA. The CD spectroscopy indicated the secondary structure of HSA is not changed in the presence of Sal B. Furthermore, The effect of metal ions (e.g. Zn(2+), Cu(2+), Co(2+), Ni(2+), Fe(3+)) on the binding constant of Sal B-HSA complex was also discussed.     

Thermal and optical properties of ZTS single crystals in the presence of 1,10-phenanthroline (Phen)

The influence of heteroaromatic N-base (1,10-phenanthroline) (Phen), a new additive as complexing agent on tris(thiourea)zinc(II)sulphate (ZTS) crystals from aqueous solutions at 30 °C is investigated. Crystals were grown using low concentration of the dopant (0.005 M L^?1) in the aqueous growth medium and the growth promoting effect (GPE) is much greater because of an increase in the metastable zone width. High dopant concentration decreases GPE. The crystalline perfection of the grown crystals is quite good both in doped and undoped crystals as evaluated by high-resolution X-ray diffractometry (HRXRD). The diffraction curve of a typical Phen doped as-grown ZTS crystal was observed to contain a single peak indicating that the crystal does not contain any epitaxial layer on the surface or internal structural grain boundaries. Not much variation is observed in FT-IR and XRD of pure and doped ZTS. Phen depresses the NLO efficiency of ZTS. It could be ascribed due to the disturbance of charge transfer in the presence of the dopant. The grown crystals were also characterized by UV–Vis, SEM and TG–DTA techniques.     

Catalytic reduction of nitrogen dioxide with propene in the presence and absence of oxygen over various metal oxides

Over metal oxides (SiO₂, ZrO₂, Al₂O₃, MgO, La₂O₃, and CaO) with-H values of metal oxide formation higher than 700 kJ/mol, C₃H₆ reacts with NO₂ in preference to O₂.     

FTIR spectroscopic study on the interaction between a fluoroionophore and metal ions.

A fluoroionophore sensor, N-[4-(1-pyrene)butyroyl]-L-tryptophan (PLT), has been reported. It can distinguish lead ion from other 12 metal ions via forming a pyrene dimer and it exhibits a very high sensitivity (0.15 microM) in aqueous solution (Chem. Commun., 2006, 2702). When the indole moiety in PLT was changed to benzene, in forming a new fluoroionophore of N-[4-(1-pyrene)butyroyl]-L-phenylalanine (PLP), it could not form a pyrene dimer in response to Pb(2+) in water. The present study describes the spectroscopic clarification of the intrinsic differences of the binding model between PLP and PLT in binding with Pb(2+). The model shows identical chelating bidentate coordination between COO(-) and Pb(2+) both in PLP-Pb and PLT-Pb; however, there is no indication of the interaction between the phenyl ring and the metal ion or the hydrogen bonding between amide groups in PLP-Pb. These differences in the binding model between PLP-Pb and PLT-Pb illustrate that the indole ring in PLT appears to play a crucial role in the high selectivity and sensitivity of PLT to lead(II) ion.     

Equilibria in complexes ofN-heterocyclic molecules,Part XV+. Intermediates in the reaction of cyanide with transition metal tris complexes of 1,10-phenanthroline, 5-nitro-1,10-phenanthroline and 2,2'-bipyridyl

Summary The Ru(phen)₃(CN)₂ · 6 H₂O, Ru(bipy)₃(CN)₂ · 6H₂O, Fe(phen)₃(CN)₂ · H₂O and Ru(5-NO₂P)₃(CN)₂ · 2 H₂O compounds have been isolated during the reaction of the parent cations with aqueous cyanide solutions. It is evident, that in each case, attack at the ligand has taken placevia the cyanide nucleophile, though the equilibrium constant for the formation of the Reissert-type species are widely different. The implications of the findings with respect to the known reaction kinetics of the parent ions in aqueous cyanide solution are discussed.Part 14: R.D. Gillard and P.A. Williams,Transition Met. Chem., 2, 109(1977)     

Interactions between metal ions and carbohydrates. Coordination behavior of neutral erythritol to Ca(II) and lanthanide ions

The study of the sugar-metal ion interactions remains one of the main objectives of carbohydrate coordination chemistry because the interactions between metal ions and carbohydrates are involved in many biochemical processes. This paper presents a comparison of coordination structures of erythritol with alkaline-earth-metal and lanthanide chloride and nitrate in the solid state using FT-IR and X-ray diffraction. Neutral, nondeprotonated erythritol (E) reacts with CaCl(2) to give three CaCl(2)(-)erythritol (CaE(I), CaE(II), CaE(III)) complexes, showing that three of the five general features of calcium-carbohydrate complexes deduced in the reference encounter contrary examples. Different coordination structures have been observed for calcium and lanthanide chloride and nitrates. The coordination of carbohydrates to metal ions is complicated, and erythritol, chloride ions, nitrates, water molecules, and ethanol (crystallization medium and reaction solvents) have the chance to coordinate to metal ions. IR spectral results show that different lanthanide ions, from LaCl(3) to TbCl(3), have similar coordination structures with erythritol. The results show that erythritol can act as two bidentate neutral ligands (CaE(I), CaE(II), CaE(III), CaEN, PrE, NdE) or as a three-hydroxyl donor (NdEN). The IR results are consistent with the crystal structures.     

Application of differential pulse polarography for trace determination of polycytidylic acid in absence and presence of some metal ions

Summary A differential pulse polarographic method has been applied to the determination of trace concentrations of polycytidylic acid (Poly-C) in absence and presence of metal ions. The applicability of differential pulse polarography for the trace determination of the investigated biological compound was examined with regard to the dependence of differential pulse current on various parameters such as pH, pulse amplitude, scan rate and drop time. The selectivity of this technique for the determination of binary and a ternary mixtures of poly-C and some metal ions has been also reported. Limits of detection and quantitation have been calculated for the differential pulse polarographic determination of the poly-C and various metal ions. The validity of this method is supported by the constancy of the i_p/C values and a statistical analysis is included on calibration curve parameters and observed concentration.     

Rearrangement of 2-(2-thienyl)benzothiazoline in the presence of thiophilic metal ions

2-(2-thienyl)Benzothiazoline and 2-(2thienyl)benzothiazol have been synthesized and characterized by several techniques (IR, NMR, UV-VIS, MS) and elemental analysis. The reactions of a solution of 2-(2thienyl)benzothiazoline with Zn, Cd, Hg(II) and Pb(II) ions have been studied. The spectral studies of the isolated complexes showed that the arrangement of the benzothiazoline to the Schiff base, N-2-mercaptophenyl-2′-methyleneimine, had occurred. The factors influencing this arrangement are discussed. Several complexes of 2-(2-pyridyl)benzothiazoline with Cd and Pb(II) were synthesized for purposes of comparison.