Search results for "LV"
showing 10 items of 13520 documents
Supramolecular open-framework architectures based on dicarboxylate H-bond acceptors and polytopic cations with three/four N–H+donor units
2015
International audience; Supramolecular assemblages based on anionic H-acceptors and cationic H-donors have been envisioned to elaborate open frameworks maintained by ionic H-bonds. Combinations of di-anionic chloranilate (CA2-), oxalate (Ox2-), or terephthalate (BDC2-) and trisimidazolium or tetrapyridinium derivatives (three and four N-H+ donors, respectively) yielded five architectures of formulae [(H3TrIB)(CA)1.5[middle dot]2DMF[middle dot]2.5H2O] (1), [(H4Tetrapy)(CA)2[middle dot]3DMF] (2), [(H3TrIB)(HOx)(Ox)[middle dot]5H2O] (3), [(H4Tetrapy)(Ox)2[middle dot]5H2O] (4), and [(H4Tetrapy)(BDC)2(H2O)[middle dot]1DMF[middle dot]3H2O] (5) (with TrIB = 1,3,5-trisimidazolylbenzene and Tetrapy …
Cis- and trans molybdenum oxo complexes of a prochiral tetradentate aminophenolate ligand : Synthesis, characterization and oxotransfer activity
2020
Abstract Reaction of [MoO2Cl2(dmso)2] with the tetradentate O2N2 donor ligand papy [H2papy = N-(2-hydroxybenzyl)-N-(2-picolyl)glycine] leads to formation of the dioxomolybdenum(VI) complex [MoO2(papy)] (1) as a mixture of cis and trans isomers. Recrystallization from methanol furnishes solid cis-1, whereas the use of a dichloromethane-hexane mixture allows for the isolation of the trans-1 isomer. Both isomers have been structurally characterized by X-ray crystallography and the energy difference between the isomeric pair has been investigated by electronic structure calculations. Optimization of two configurational isomers in the gas phase predicts the trans isomer to lie 2.5 kcal/mol lower…
2-Methyltetrahydrofuran: A Green Solvent for Iron-Catalyzed Cross-Coupling Reactions
2018
Iron‐catalyzed cross‐coupling reactions allow sustainable formation of C−C bonds using cost‐effective, earth‐abundant base‐metal catalysis for complex syntheses of pharmaceuticals, natural products, and fine chemicals. The major challenge to maintain full sustainability of the process is the identification of green and renewable solvents that can be harnessed to replace the conventional solvents for this highly attractive reaction. Herein, iron‐catalyzed cross‐coupling of aryl chlorides and tosylates with challenging organometallic reagents possessing β‐hydrogens is found to proceed in good to excellent yields with the green, sustainable, and eco‐friendly 2‐methyltetrahydrofuran (2‐MeTHF) a…
Hydrogen-Bonded Open-Framework with Pyridyl-Decorated Channels: Straightforward Preparation and Insight into Its Affinity for Acidic Molecules in Sol…
2017
International audience; An hydrogen-bonded open framework with pores decorated by pyridyl groups has been constructed following an off-charge-stoichiometry assemblage of protonated tetrakis(4-pyridyl-oxymethyl)methane and [Al(oxalate)3]3-, respectively the H-bond donor and acceptor of the ionic H-bond interactions. This supramolecular porous architecture (SPA-2) possesses 1 nm-large pores interconnected in 3D with high solvent accessible void (53%). It demonstrated remarkable affinity for acidic organic molecules in solution, which was investigated by the means of various carboxylic acids including larger drug molecules. Noteworthy, competing sorption between acetic acid and its halogenated…
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…
Acylchalcogenourea Complexes of Silver(I)
2016
Acylthio- or acylselenoureas react with silver(I) oxide to form tetranuclear silver(I) complexes containing the deprotonated acylchalcogenourea ligands bound to the silver atoms through the chalcogen and oxygen atoms. These tetrasilver(I) species react with either 4 or 8 equiv. of a phosphine to afford either dinuclear silver(I) phosphine complexes or tetrahedral silver diphosphine complexes. In these compounds, the acylchalcogenourea ligands form six-membered rings by coordinating to the metal atom through the chalcogen and oxygen atoms. In one case, we observed a very rare example of an acylthiourea ligand coordinated through the nitrogen and sulfur atoms to form a four-membered ring. A 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)…
A new chiral dimanganese(iii) complex: synthesis, crystal structure, spectroscopic, magnetic, and catalytic properties
2016
Two enantiomeric complexes of formula [MnIII2(μ-OCH3)2(R-valBINAM)2]·1.75DMF (1) and [MnIII2(μ-OCH3)2(S-valBINAM)2]·2DMF (2) [valBINAM = 1,1′-binaphthalene-2,2′-bis(3-methoxysalicylideneiminate)] have been synthesized using as a ligand the chiral Schiff bases resulting from the condensation reactions between o-vanillin and the chiral 1,1′-binaphthyl-2,2′-diamine. The structures of 1 and 2 which have been solved by single crystal X-ray diffraction consist of neutral dimers, the manganese(III) ions being bridged by two methoxido anions, arising from the solvent, and by two valBINAM2− ligands. Their circular dichroism spectra at room temperature emphasize the occurrence of the exciton coupling…
Solvent effects on the dimensionality of oxamato-bridged manganese(II) compounds
2018
Two new oxamate-containing manganese(II) complexes, [{Mn(H2edpba)(H2O)2}2]n (1) and [Mn(H2edpba)(dmso)2]∙dmso∙CH3COCH3∙H2O (2) (H4edpba = N,N′-ethylenediphenylenebis(oxamic acid) and dmso = dimethylsulfoxide), have been synthesized and the structures of 1 and 2 were characterized by single crystal X-ray diffraction. The structure of 1 consists of neutral honeycomb networks in which each manganese(II) is six-coordinate by one H2edpba2− ligand and two carboxylate–oxygens from two other H2edpba2− ligands building the equatorial plane. Each manganese is connected to its nearest neighbor through two carboxylate(monoprotonated oxamate) bridges in an anti-syn conformation. A dmso solution of singl…
CuII2, CuII4 and CuII6 complexes with 3-(2-pyridyl)pyrazolate. Structure, magnetism and core interconversion
2019
Abstract Reactions of stoichiometric amounts of L1(−) (HL1 = 3-(2-pyridyl)pyrazole) with [Cu(H2O)6](ClO4)2, with or without PhCO2−, in MeOH or N,N′-dimethylformamide (dmf), led to the isolation of three copper(II) complexes of varying nuclearity, [CuII2(L1)2(ClO4)2(MeOH)2] (1), [CuII4(L1)4(O2CPh)2(MeOH)4](ClO4)2·2H2O (2) and [CuII6(L1)6(O2CPh)2(ClO4)2(dmf)4](ClO4)2·2dmf·2H2O (3). Structural analysis reveals two centrosymmetric four-coordinate {CuII(L1)(ClO4)(MeOH)} units are dipyrazolate-bridged in 1, giving rise to a square-pyramidal (SP; τ = 0.13) coordination to the CuII ion. In 2, two centrosymmetric four-coordinate dipyrazolate-bridged {CuII2(μ-L1)2(MeOH)2}2+ units in two layers are he…