Synthesis, crystal structures and magnetic behavior of two 3D coordination polymers using N-(4/3-arboxyphenyl)iminodiacetic acids as bridging ligands

Research on structure and magnetic properties of polynuclear metal complexes to understand the structural and chemical factors governing the electronic exchange coupling mediated by multi-atom bridging ligands is of growing interest. Hydrothermal treatment of Ni(NO3)(2)center dot 6H(2)O with N-(4-carboxyphenyl)iminodiacetic acid N-4(H(3)CPIDA)] at 150 degrees C yielded a 3D coordination polymer of general formula Ni-3{N-4( CPIDA)}(2)(H2O)(3)]center dot 6H(2)O (1). An analogous network of general formula Co-3{N-3(CPIDA)}(2)(H2O)(3)]center dot 3H(2)O (2) was synthesized using N-(3-carboxyphenyl) iminodiacetic acid N-3(H(3)CPIDA)] in combination with Co(NO3)(2)center dot 6H(2)O under identical reaction condition. Both the complexes contain trinuclear secondary building unit, and crystallized in monoclinic system with space groups C2/c (1) and P2(1)/c (2), respectively. Variable temperature magnetic characterization of these complexes in the temperature range of 2-300 K indicated the presence of overall ferromagnetic and antiferromagnetic behavior for 1 and 2, respectively. Density functional theory calculations (B3LYP functional) were performed for further insight on the trinuclear units to provide a qualitative theoretical interpretation on the overall magnetic behavior of the complexes 1 and 2. (C) 2010 Elsevier B.V. All rights reserved.

Crystallographic identification of a ‘stepped-cubane’ structure for the Cu4O4 core in [Cu4L2(bipy)4(µ3-OH)2][ClO4]4(HL = 5-hydroxy-6-methylpyridine-,4-dimethanol, bipy = 2,2′-bipyridine)

The structure of [Cu4L2(bipy)4(µ3-OH)2][ClO4]4 containing a Vitamin B6 ligand, pyridoxine (5-hydroxy-6-methylpyridine-3,4-dimethanol, HL), and 2,2′-bipyridine (bipy) has been determined by single-crystal X-ray analysis. This is the first report on a copper(II) complex having a ‘stepped-cubane’ structure. The compound crystallizes in the triclinic space group P[1 with combining macron](Z= 1) with a= 11.015(3), b= 11.902(1), c= 13.142(2)Å, α= 105.07(1), β= 102.22(1) and γ= 99.12(1)°; R= 0.054). The co-ordination geometry around each copper is trigonally distorted square pyramidal. Two of the basal sites are occupied by bipyridyl nitrogens in a bidentate fashion. The remaining basal positions for Cu(1) are filled by a phenolic oxygen and a 4-hydroxymethyl oxygen of the L moiety, whereas for Cu(2) they are occupied by two µ3-OH oxygens. The axial sites are occupied by a µ3-OH oxygen and the 4-hydroxymethyl oxygen of the same pyridoxine for Cu(1) and Cu(2), respectively. Both the bridging nature of the 4-hydroxymethyl oxygen of the L moiety and the unsymmetrical bridging nature of the µ3-OH groups with axial–equatorial bridging are novel features. The structure is discussed in relation to stepped-cubane structures reported in the literature. A comparative study is also made with µ3-hydroxo-bridged copper(II) complexes. Both the plasticity effect of CuII and the stacking interactions between the various rings appear to be important in stabilizing this unusual structure.

The first structurally characterized diruthenium(II,III) complex with four bridging arylcarboxylato ligands

The diruthenium(II,III) compound [Ru2Cl(O2CC6H4-p-OMe)4](H2O)0.25 (1) has been prepared and its crystal structure determined by X-ray studies. The crystals belong to the triclinic space group, PImage , and the asymmetric unit consists of one full dimer and two half dimers. The {Ru2(O2CC6H4-p-OMe)4+} units are bridged by chloride ions into an infinite zigzag chain, with an average Ru---Cl distance and Ru---Cl---Ru angle of 2.567(2) Å and 121.0(1)°, respectively. The average Ru---Ru distance of 2.286(1) Å in 1 is comparable with that in analogous tetra-alkylcarboxylates, Ru2Cl(O2CR)4 and tetra-amidates, Ru2Cl(ArCONH)4.

Mixed ligand cobalt(III) complexes of tetradentate N,N′-ethylenebis(acetylacetonimine) and flexidentate isonitroso-β-diketones and isonitrosomonoketones

A series of mixed ligand cobalt(III) complexes having the general formula Co(EA)X [where EA = dianion of N,N′-ethylenebis(acetylacetonimine) and X = anion of isonitroso-acetylacetone, IAA; isonitrosobenzoylacetone, IBA; isonitrosodibenzoylmethane, IDBM; isonitrosoethylacetoacetate, IEA; isonitrosoacetoacetanillide, IAN; isonitrosoethylmethylketone, IEMK; isonitrosobenzylmethylketone, IBMK and isonitrosopropiophenone, IPP] have been synthesised and characterised. A facial-cis-β structure (cis with respect to the coordinated two oxygen atoms of EA) with N,N,N,O,O,O ligational environment has been assigned for the complexes. The characterisation of the complexes has been based upon chemical analysis, electrical conductivity, magnetic moment, IR, PMR and electronic spectra.

Coated pits,endosome CURLing and intracellular receptor--ligand trafficking

In mediating endocytosis of extracellular macromolecules; the major mechanism in which cells ingest nutrients, degrade hormones and maintain the protein and lipid compositions of their organelle membrane, the cell surface receptors encounter 'coated pits', migrate continuously from one organelle to another, deliver the 'cargo' and often recycle back to the cell surface. This article is an attempt to give an account of the recent advances in our understanding of the molecular events involved in the 'round trip itinerary' of cell surface receptors.

Double helix conformation, groove dimensions and ligand binding potential of a G/C stretch in B-DNA

The self-complementary DNA fragment CCGGCGCCGG crystallizes in the rhombohedral space group R3 with unit cell parameters a = 54.07 angstrom and c = 44.59 angstrom. The structure has been determined by X-ray diffraction methods at 2.2 angstrom resolution and refined to an R value of 16.7%. In the crystal, the decamer forms B-DNA double helices with characteristic groove dimensions: compared with B-DNA of random sequence, the minor groove is wide and deep and the major groove is rather shallow. Local base pair geometries and stacking patterns are within the range commonly observed in B-DNA crystal structures. The duplex bears no resemblance to A-form DNA as might have been expected for a sequence with only GC base pairs. The shallow major groove permits an unusual crystal packing pattern with several direct intermolecular hydrogen bonds between phosphate oxygens and cytosine amino groups. In addition, decameric duplexes form quasi-infinite double helices in the crystal by end-to-end stacking. The groove geometries and accessibilities of this molecule as observed in the crystal may be important for the mode of binding of both proteins and drug molecules to G/C stretches in DNA.

Bridging the Ruddlesden–Popper and the Dion–Jacobson series of layered perovskites: synthesis of layered oxides, A2–xLa2Ti3–xNbxO10(A = K, Rb), exhibiting ion exchange

Solid solutions of the formula, A2–xLa2Ti3–xNbxO10(A = K, Rb), exist for the range 0[less-than-or-eq]x[less-than-or-eq]1.0, bridging n= 3 members of the Ruddlesden–Popper series (A2La2Ti3O10) and the Dion–Jacobson series (ALa2Ti2NbO10). For 0[less-than-or-eq]x[less-than-or-eq]0.75, the phases possess body-centred structures characteristic of the Ruddlesden–Popper phases, while the x= 1 members are isostructural with KCa2Nb3O10(A = K) and CsCa2Nb3O10(A = Rb). Protonated derivatives, H2–xLa2Ti3–xNbxO10, which are prepared by ion exchange, retain the structural difference of the parent phases. A difference in the Brønsted acidity of the protonated derivatives revealed by intercalation experiments with organic bases seems to be related to this structural difference.

Reactions of copper(I) aryloxides with phenyl isothiocyanate: steric and ligand control in the oligomerization of [N-phenylimino(aryloxy)methanethiolato]copper(I) complexes

The preparation of five different copper(I) complexes [CuSC(=NPh)(OAr)}L(n)]m (1-5) formed by the insertion of PhNCS into the Cu-OAr bond and the crystal structure analyses of three of them have been carried out. A monomeric species 1 (OAr = 2,6-dimethylphenoxide) is formed in the presence of excess PPh3 (n = 2, m = 1) and crystallizes as triclinic crystals with a = 12.419(4) angstrom, b = 13.298(7) angstrom, c = 15.936(3) angstrom, alpha = 67.09(3)-degrees, beta = 81.63(2)-degrees, gamma = 66.54(3)-degrees, V = 2224(2) angstrom3, and Z = 2. The structure was refined by the least-squares method to final R and R(w) values of 0.038 and 0.044, respectively, for 7186 unique reflections. Copper(I) 2,5-di-tert-butyl-4-methylphenoxide results in the formation of a dimeric species 2 in the presence of P(OMe)3 (n = 1, m = 2), where the coordination around Cu is trigonal. Crystals of 2 were found to be orthorhombic with a = 15.691(2) angstrom, b = 18.216(3) angstrom, c = 39.198(5) angstrom, v = 11204(3) angstrom3, and Z = 8. Least-squares refinement gave final residuals of R = 0.05 and R(w) = 0.057 with 6866 unique reflections. A tetrameric species 3 results when PPh3 is replaced by P(OMe)3 in the coordination sphere of copper(I) 2,6-dimethylphenoxide. It crystallizes in the space group P1BAR with a = 11.681 (1) angstrom, b = 13.373(2) angstrom, c = 20.127(1) angstrom, a = 88.55(l)-degrees, beta = 89.65(l)-degrees, gamma = 69.28(1)-degrees, V = 2940(l) angstrom3, and Z = 2. Least-squares refinement of the structure gave final values of 0.043 and 0.05 for R and R(w) respectively using 12214 unique reflections. In addition, a dimeric species 4 is formed when 1 equiv of PPh3 is added to the copper(I) 4-methylphenoxide, while with an excess of PPh3 a monomeric species 5 is isolated. Some interconversions among these complexes are also reported.

Stereochemical properties and x-ray structure of a water-soluble diastereomeric (arene)ruthenium(II) Schiff-base complex: [Ru(.eta.-MeC6H4Pri-p)(H2O)(L*)](ClO4), containing a weakly bound aqua ligand [HL* = (S)-(.alpha.-methylbenzyl)salicylaldimine]

An air-stable and water-soluble diastereomeric half-sandwich ruthenium(I1) complex, [Ru(s-MeCsH4Pr'-p)(H*O)-(L*)] (C104) (l), has been isolated and structurally characterized [HL* = (27)-(a methylbenzyl)salicylaldimine,2-HOC6H4CH-NCHMePhI. Complex 1, Czd-I3oNO&lRu, crystallizes in the noncentric triclinic space group P1 with a = 9.885(1) A, b = 10.185(1) A, c = 14.187(2) A, a = 110.32(1)', 6 = 102.17(1)', y = 102.41(1)O, V=1243( 1) A3, and 2 = 2. The X-ray structure shows the presence of two diastereomers in a 1:l ratio having RR,,,SCand SR,,,&c onfigurations. The Ru-OHz bond distances are considerably long, and the values for RR, - a~n d SRu-1isomers are 2.1 19(5) and 2.203(5) A, respectively. The aqua complex (1) exists as a single diastereomer in solution,and it forms stable adducts with P-, N-, and halide-donor ligands. The stereochemical changes associated with adduct-forming reactions follow an inversion order: PPhs >> P(OMe)3 > pyridine bases >> halides (I, Br, Cl) >H20.

Computation of restoration of ligand response in the random kinetics of a prostate cancer cell signaling pathway

Mutation and/or dysfunction of signaling proteins in the mitogen activated protein kinase (MAPK) signal transduction pathway are frequently observed in various kinds of human cancer. Consistent with this fact, in the present study, we experimentally observe that the epidermal growth factor (EGF) induced activation profile of MAP kinase signaling is not straightforward dose-dependent in the PC3 prostate cancer cells. To find out what parameters and reactions in the pathway are involved in this departure from the normal dose-dependency, a model-based pathway analysis is performed. The pathway is mathematically modeled with 28 rate equations yielding those many ordinary differential equations (ODE) with kinetic rate constants that have been reported to take random values in the existing literature. This has led to us treating the ODE model of the pathways kinetics as a random differential equations (RDE) system in which the parameters are random variables. We show that our RDE model captures the uncertainty in the kinetic rate constants as seen in the behavior of the experimental data and more importantly, upon simulation, exhibits the abnormal EGF dose-dependency of the activation profile of MAP kinase signaling in PC3 prostate cancer cells. The most likely set of values of the kinetic rate constants obtained from fitting the RDE model into the experimental data is then used in a direct transcription based dynamic optimization method for computing the changes needed in these kinetic rate constant values for the restoration of the normal EGF dose response. The last computation identifies the parameters, i.e., the kinetic rate constants in the RDE model, that are the most sensitive to the change in the EGF dose response behavior in the PC3 prostate cancer cells. The reactions in which these most sensitive parameters participate emerge as candidate drug targets on the signaling pathway. (C) 2011 Elsevier Ireland Ltd. All rights reserved.

Ce0.98Pd0.02O2-delta: Recyclable, ligand free palladium(II) catalyst for Heck reaction

Palladium substituted in cerium dioxide in the form of a solid solution, Ce-0.98 Pd-0.02 O-1.98 is a new heterogeneous catalyst which exhibits high activity and 100% trans-selectivity for the Heck reactions of aryl bromides including heteroaryls with olefins. The catalytic reactions work without any ligand. Nano-crystalline Ce-0.98 Pd-0.02 O-1.98 is prepared by solution combustion method and Pd is in +2 state. The catalyst can be separated, recovered and reused without significant loss in activity.

Variations in the copper(I)-copper(I) distances in multinuclear clusters with identical coordination geometries. Short metal-metal contacts induced by oligomerization

Factors contributing to the variations in the Cu(I)-Cu(I) distances in two clusters with identical ligand and coordination geometries have been analyzed. While the hexamer, 4, exhibits metal-metal distances in the range 2.81-3.25 Angstrom, shorter contacts are found in the corresponding tetramer, 3 (2.60-2.77 Angstrom). EHT calculations reveal relatively little attractive interactions in the corresponding Cu-4(4+) and Cu-6(6+) cores. Introduction of the ligands lowers the reduced overlap populations between the metals further. MNDO calculations with model electrophiles have been carried out to determine the bite angle requirements of the ligands. These are satisfactorily met in the structures of both 3 and 4. The key geometric feature distinguishing 3 and 4 is the Cu-S-Cu angle involving the bridging S- unit. In 4, the corresponding angles are about 90 degrees, while the values in 3 are smaller (70-73 degrees). Wider angles are computed to be energetically favored and are characterized by an open three-center bond and a long Cu-Cu distance. The bridging angles are suggested to be primarily constrained by the mode of oligomerization. Implications of these results for the stability and reactivity of these clusters and for short metal-metal distances in d(10) systems in general are discussed.

High-Throughput Study of the Cu(CH3COO)(2)center dot H2O-5-Nitroisophthalic Acid Heterocyclic Ligand System: Synthesis, Structure, Magnetic, and Heterogeneous Catalytic Studies of Three Copper Nitroisophthalates

A high-throughput screening was employed to identify new compounds in Cu(CH3COO)(2)center dot H2O-NIPA-heterocyclic ligand systems. Of the compounds identified, three compounds, Cu-3{(NO2)-C6H3-(COO)(2)}(3)(C3N6H6)] (1), Cu-2(mu(3)-OH)(H2O){(NO2)-C6H3-(COO)(2)}(CN4H)]center dot-(H2O) (II), and Cu-2(mu(3)-OH)(H2O){(NO2)-C6H3-(COO)(2}-)(CN5H2)]center dot 2(H2O) (III), have been isolated as good quality single crystals by employing conventional hydrothermal methods. Three other compounds, Cu-2{(NO2)-C6H3-(COO)(2)}-(CN4H)(H2O) (IIa), Cu-2{(NO2)-C6H3-(COO)(2)}(CN5H2) (IIIa), and Cu-2{(NO2)-C6H3-(COO)(2)}{(CN5H2)(2)}2H(2)O (IIIb), were identified by a combination of elemental analysis, thermogravimetric analysis (TGA), and IR spectroscopic studies, although their structures are yet to be determined. The single crystalline compounds were also characterized by elemental analysis, TGA, IR, UV vis, magnetic, and catalytic studies. The structures of the compounds have paddle wheel (I) and infinite Cu 0(H) Cu chains (II and HI) connected with NLPA and heterocyclic ligands forming two-(II) and three-dimensional (I and III) structures. The bound and lattice water molecules in 11 and 111 could be reversibly removed/inserted without affecting the structure. In the case of II, the removal of water gives rise to a structural transition, but the dehydrated phase reverts back to the original phase on prolonged exposure to atmospheric conditions. Magnetic studies indicate an overall antiferromagnetism in all of the compounds. Lewis acid catalytic studies indicate that compounds II and HI are active for cyanosilylation of imines.

Di- and tri-metallic complexes containing two bridging cyclodiphosphazane ligands: the crystal structure of [MO2(CO)8{µ-cis-[PhNP(OC6H4Me-p)]2}2]

The reactions of the mononuclear cyclodiphosphazane complexes, cis-[Mo(CO)(4){cis-[PhNP(OR)](2)}(2)] with [Mo(CO)(4)(nbd)] (nbd = norbornadiene). [Mo(CO)(4)(NHC5H10)(2)] or [MCl(2)(cod)] (cod = cycloocta-1,5-diene) afforded the homobimetallic complexes; [Mo-2(CO)(8){mu-cis-[PhNP(OR)](2)}(2)] (R = C(5)H(4)Me-p 5 or CH2CF3 6) or the heterobimetallic complexes. [Mo-2(CO)(8){mu-cis-[PhNP(OE)](2)}(2)MCl(2)] (R = C(6)H(4)Me-p; M = Pd 7 or Pt 8). In all the above complexes, the two metal moieties are bridged by two cyclodiphosphazane ligands. The reactions of the mononuclear complexes, cis-[M(CO)(4)(A){cis-[PhNP(OC(6)H(4)Me-p)](2)}] with (M'Cl-2(cod)] afforded the trinuclear complexes, cis-[M'Cl-2[M(CO)(4)(A){cis-[PhNP(OC(6)H(4)Me-p)](2)}](2)] (M' = Pd, M = Mo, A = P(OMe)(3) 10; M' = Pt, M = Mo. A = P(OMe)(3) 11; M' = Pd. M = W. A = NHC5H10 12; M' = Pt, M = W. A = NHC5H10 13). The structure of the complex 5 has been determined by single-crystal X-ray crystallography.