Search results for "CRYSTAL"
showing 10 items of 22886 documents
Ion-Pair Complexation with Dibenzo[21]Crown-7 and Dibenzo[24]Crown-8 bis-Urea Receptors
2016
Synthesis and ion-pair complexation properties of novel ditopic bis-urea receptors based on dibenzo[21]crown-7 (R(1) ) and dibenzo[24]crown-8 (R(2) ) scaffolds have been studied in the solid state, solution, and gas phase. In a 4:1 CDCl3 /[D6 ]DMSO solution, both receptors clearly show positive heterotropic cooperativity toward halide anions when complexed with Rb(+) or Cs(+) , with the halide affinity increasing in order I(-) <Br(-) <Cl(-) . In solution, the rubidium complexes of both receptors have higher halide affinities compared to the caesium complexes. However, Rb(+) and Cs(+) complexes of R(2) show stronger affinities toward all the studied anions compared to the corresponding catio…
Protonation of a Spherical Macrotricyclic Tetramine: Water Inclusion, Allosteric Effect, and Cooperativity
2017
The spherical macrotricyclic cryptand tetramine "C24" (1) displays remarkable protonation behaviour. It undergoes protonation in four successive steps for which pKa values of 11.17±0.05, 10.28±0.04, 6.00±0.06 and 3.08±0.08 have been determined at 298 K. The unusually close values for the first two protonations provide evidence for the encapsulation of a water molecule serving as effector for the second protonation, which is consistent with earlier observations that the exchange of protons bound in the diprotonated species with solvent protons is unusually slow and that 17 O NMR spectra show the presence of an oxygen centre in the same species quite distinct from that of solvent water. Encap…
The separation of cis- and trans-1,3-cyclohexanediol isomers by copper complexation. Crystal structures of cis-1,3-cyclohexanediol and copper(II) chl…
2002
Abstract A 1:1 complex between copper(II) chloride and cis-1,3-cyclohexanediol has been synthesized and its crystal structure determined. The structure is composed of two different dinuclear [CuCl2(c-13chd)]2 units in which the copper(II) ions are surrounded by the two oxygen atoms of the diol and the two halide ions in a distorted cis-square planar arrangement in both cases. A fifth coordination site is occupied by a halide ion in one dinuclear unit for both copper ions and an O atom belonging to the adjacent CuCl2(c-13chd) moiety in the other dinuclear unit for both copper ions, thus forming a distorted square pyramidal geometry for the metals in all cases. The ability of CuCl2 to prefere…
Enhancement of the Intermolecular Magnetic Exchange through Halogen···Halogen interactions in Bisadeninium Rhenium(IV) Salts
2017
Two novel ReIV salts of general formula [H2ade]2[ReIVX6]X2·4H2O [H2ade2+ = 9H-adenine-1,7-diium; X = Cl(1) and Br(2)] have been synthesized and magneto-structurally characterized. 1 and 2 are isostructural salts that crystallize in the orthorhombic system with space group Fdd2. Both compounds are made up of discrete mononuclear [ReIVX6]2- and X- anions and doubly protonated adenine cations. The six-coordinate rhenium(IV) ion is bonded to six halide ligands [X = Cl (1) and Br (2)] in an octahedral geometry. Short intermolecular ReIV−X···X−ReIV interactions, as well as ReIV−X···H−N(H2ade) and ReIV−X···H−Ow hydrogen bonds, are present in the crystal lattice of 1 and 2. Magnetic suscep-tibility…
A comparative study of methanol carbonation on unsupported SnO2 and ZrO2
2009
International audience; The aim of this work was to explore the catalytic properties of SnO2 in the coupling of methanol with carbon dioxide to afford dimethyl carbonate. SnO2 nanopowders were produced by hydrolysis of tin tetra-tert-butoxide dissolved in n-butanol. The samples were much more active than a commercial one due to their higher surface areas. In addition, they exhibited excellent recyclability. However, comparison with ZrO2, prepared and tested under the same experimental conditions, showed that zirconia-based catalysts were more selective and are, among the heterogeneous catalysts already reported, still the more selective. SnO2 also catalyzed the formation of dimethyl ether l…
Synthesis, Crystal Structure and Magnetic Properties of Heteropolynuclear Re IV M II Complexes Based on the Robust [ReCl 5 (pyzCOO)] 2– Unit (pyzCOO …
2016
The syntheses, crystal structures and magnetic properties of four rhenium(IV) compounds of formulae NBu4[ReCl5(pyzCOOH)]·H2O (1), [ReCl5(µ-pyzCOO)M(dmphen)2]·2CH3CN [M = Ni (2) and Co (3)] and {[ReCl5(µ3-pyzCOO)]2Mn2(dmphen)3}n (4) (NBu4 = tetra-n-butylammonium cation, pyzCOOH = 2-pyrazinecarboxylic acid, dmphen = 2,9-dimethyl-1,10-phenanthroline) are reported herein. Compound 1 was obtained by the reaction of NBu4[ReCl5(dmf)] (dmf = dimethylformamide) with pyzCOOH in acetone, whereas the other complexes were obtained by the reaction of 1 with M(ClO4)2·6H2O [M = Ni (2), Co (3), Mn (4)] and dmphen in acetonitrile. Complex 1 is a mononuclear compound, 2 and 3 are neutral heterodinuclear compl…
Linking PO43− and HAsO42− anions with a dinuclear [ZnII2] complex: Formation and stabilization of novel decanuclear metallomacrocyclic [ZnII10] and t…
2017
The linkage of PO43- and HAsO42--anions with a newly synthesized five-coordinate dinuclear zinc complex, Zn-2(cpdp)(H2O)(2)]Cl (1) H(3)cpdp =N,N'-bis2-carboxybenzomethyl]-N,N'-bis2-pyridylmethyl]-1,3diamino propan-2-ol], has been explored. In methanol-water, the reaction of 1 with Na2HPO4 center dot 2H(2)O and Na2HAsO4 center dot 7H(2)O/NaBr separately, at ambient temperature, yielded the novel phosphate-bridged decanuclear zinc cluster, (H3O)(4)Zn-10(cPdP)(4)(mu(5)-PO4)(2)(H2O)(6)](6 center dot Cl)center dot 53H(2)O (2) and hydrogen arsenate bridged tetranuclear zinc cluster, Na-2Zn-4(cpdp)(2)(mu(4)-HAsO4)]ClBr center dot 13H(2)O (3), respectively. Analysis of the single crystal X-ray stru…
Insights into the crystal packing of phosphorylporphyrins based on the topology of their intermolecular interaction energies
2014
Four metal complexes of 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin 1M (M = Cd(II), Ni(II), Pd(II), and Pt(II)) were synthesized and crystallographically characterized. The crystal organization patterns were analyzed using DFT (B97-D3/def2-SVP) calculations of the intermolecular interaction energies between complexes in the crystals. For the systematic analysis of crystal packing, the calculations were extended to previously reported compounds 1M (M = H2, Cu(II), and Zn(II)). Quantitative analysis of the interaction energies shows the essential role of weak intermolecular interactions, such as C-H⋯O, C-H⋯π and M⋯π, in the formation of basic structural motifs and their organization …
Synthesis and structural characterization of well-defined bis(oxamato)palladate(II) precatalysts for Suzuki and Heck reactions
2018
Abstract A family of tetra-n-butylammonium salts of bis(oxamato)palladate(II) complexes of formula (n-Bu4N)2[Pd(Lm)2]·pH2O [m = 1–9; L1 = N-phenyloxamate (pma) and p = 2 (1), L2 = N-2-methylphenyloxamate (2-Mepma) and p = 4 (2), L3 = N-4-methylphenyloxamate (4-Mepma) and p = 2 (3), L4 = N-2,3-dimethylphenyloxamate (2,3-Me2pma) and p = 3 (4), L5 = N-2,4-dimethylphenyloxamate (Me2pma) and p = 4 (5), L6 = N-2,5-dimethylphenyloxamate (2,5-Me2pma) and p = 7 (6), L7 = N-3,4-dimethylphenyloxamate (3,4-Me2pma) and p = 6 (7), L8 = N-3,5-dimethylphenyloxamate (3,5-Me2pma) and p = 5 (8)] have been prepared and characterized by spectroscopic methods. The crystal structure of 1 that has been solved by s…
Modulation of the ordering temperature in anilato-based magnets
2019
Abstract Four new 2D honeycomb anilato-based ferrimagnets with Mn(II) and Cr(III) have been prepared and characterized. These compounds, formulated as (NBu4)[MnCr(C6O4X2)3(PhCHO)]·PhY (X/Y = Cl/H (1), Br/H (2), Cl/CHO (3) and Br/CHO (4) show that it is possible to include benzaldehyde as a co-ligand coordinated to the Mn(II) metal atom in these 2D ferrimagnets. This inclusion increases the coordination number of Mn(II) to seven resulting in a change in the ordering temperatures of these 2D ferrimagnets (from ca. 10–11 K to ca. 7 K). Here we show the role played by the additional benzaldehyde ligand and by the crystallization solvent molecules (benzene in 1 and 2 and benzaldehyde in 3 and 4)…