Search results for "LEM"

Deprotonation of Benzoxazole and Oxazole Using Lithium Magnesates

2005

International audience; The first deprotonations of oxazole and benzoxazole using lithium magnesates are described. The reactions occurred in tetrahydrofuran at room temperature using 1/3 equiv of lithium tributylmagnesate. As 2-lithiooxazole and 2-lithiobenzoxazole, lithium tri(2-oxazolyl)magnesate and lithium tri(2-benzoxazolyl)magnesate very rapidly and completely isomerized to the more stable 2-(isocyano)enolate and 2-(isocyano)phenolate type structures, respectively, a result shown by NMR analysis. The isolation of 2-substituted oxazoles and benzoxazoles in medium to good yields after electrophilic trapping was interpreted in two ways:  (1) the equilibration between the open and closed…

Electrochemical meso-functionalization of magnesium(II) porphine

2010

International audience; Regioselective meso-functionalization of the totally unsubstituted magnesium(II) porphine was performed by controlled potential electrolysis with pyridine and triphenylphosphine as nucleophiles leading to the original pyridinium and phosphonium substituted derivatives, respectively. The crystallographic structure of the latter is described as the only meso-phosphonium porphyrin reported to date.

Diastereoselectivity of the Addition of Propargylic Magnesium Reagents to Fluorinated Aromatic Sulfinyl Imines.

2021

The addition of propargylmagnesium bromide to fluorinated aromatic sulfinyl imines gave homopropargyl amines with total regio- and diastereoselection. Complete reversal of diastereoselectivity can be achieved in some cases using coordinating (THF) or noncoordinating (DCM) solvents. Substituted propargylic magnesium reagents have been also tested toward fluorinated aryl sulfinyl imines affording chiral homoallenyl amines with good yields and selectivity control. DFT calculations helped to rationalize the origin of the experimental regio- and diastereoselectivities observed in each case.

A carboxylate-bridged NiII8 cluster with a distorted cubane topology: structure, magnetism and density functional studies

2016

Using a dicarboxylate ligand appended with (2-pyridyl)ethylamine unit, a new cluster [NiII8(L4)6(DMF)2(CH3OH)2(H2O)6][ClO4]4·2CH3OH·2CH3CO2C2H5 (1) [L4(2−): 3-[N-{2-(pyridin-2-yl)ethyl}amino]-bis(propionate)] has been synthesized, through ‘coordination-driven self-assembly’. The crystal structure of 1 reveals a centrosymmetric octanuclear carboxylate-bridged nickel(II) tetracation, with a distorted cubane topology. The four crystallographically independent nickel(II) centres differ markedly in their coordination environment. Magnetic studies (2–300 K) reveal that in 1 the net magnetic-exchange is antiferromagnetic. Based on geometric parameters associated with two interacting nickel(II) cen…

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…

Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations.

2019

The present study introduces a comprehensive exploration in terms of physicochemical characterization and calculations based on density functional theory with Hubbard's correction (DFT+U) of the whole family of α-Co(II) hydroxyhalide (F, Cl, Br, I). These samples were synthesized at room temperature by employing a one-pot approach based on the epoxide route. A thorough characterization (powder X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis/mass spectroscopy, and magnetic and conductivity measurements) corroborated by simulation is presented that analyzes the structural, magnetic, and electronic aspects. Beyond the inherent tendency of intercalated anions to …

A Selenium-Nitrogen Chain with Selenium in Different Oxidation States

2017

Size‐Selective Encapsulation of Hydrophobic Guests by Self‐Assembled M 4 L 6 Cobalt and Nickel Cages

2012

Subtle differences in metal-ligand bond lengths between a series of [M(4)L(6)](4-) tetrahedral cages, where M = Fe(II), Co(II), or Ni(II), were observed to result in substantial differences in affinity for hydrophobic guests in water. Changing the metal ion from iron(II) to cobalt(II) or nickel(II) increases the size of the interior cavity of the cage and allows encapsulation of larger guest molecules. NMR spectroscopy was used to study the recognition properties of the iron(II) and cobalt(II) cages towards small hydrophobic guests in water, and single-crystal X-ray diffraction was used to study the solid-state complexes of the iron(II) and nickel(II) cages.

Combining Amines and 3-(2-Pyridyl)-[1,2,3]Triazolo[1,5-a]pyridine: An Easy Access to New Functional Polynitrogenated Ligands

2019

Triazolopyridine-pyridine amine ligands are easily obtained by means of either thermal- or copper(II)-mediated reactions. Starting from a readily accessible iodo derivative of triazolopyridine-pyridine and different amines, this new family of compounds combines aromatic and aliphatic nitrogen atoms with promising coordinating properties. Furthermore, chemical derivatization of a new triazolopyridine-pyridine diamine compound, N1-[6-([1,2,3]triazolo[1,5-a]pyridin-3-yl)pyridin-2-yl]ethan-1,2-diamine, allows the preparation of several remote-pyridine-containing ligands.

First titanium-catalyzed 1,4-hydrophosphination of 1,3-dienes

2010

International audience