Cycloalkyl-based unsymmetrical unsaturated (U2)-NHC ligands : flexibility and dissymmetry in ruthenium-catalysed olefin metathesis.

International audienceAir-stable Ru-indenylidene and Hoveyda-type complexes bearing new unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands combining a mesityl unit and a flexible cycloalkyl moiety as N-substituents were synthesised. Structural features, chemical stabilities and catalytic profiles in olefin metathesis of this new library of cycloalkyl-based U2-NHC Ru complexes were studied and compared with their unsymmetrical saturated NHC-Ru homologues as well as a set of commercially available Ru-catalysts bearing either symmetrical SIMes or IMes NHC ligands

2-(4,5-Diphenyl-2-p-tolyl-1H-imidazol-1-yl)-3-phenyl­propan-1-ol

In the title compound, C31H28N2O, the dihedral angles formed by the imidazole ring with the three aryl substituents are 18.52 (8) and 85.56 (7) and 85.57 (7)°, respectively. In the crystal, mol­ecules are linked by O—H⋯N and C—H⋯O hydrogen bonds into chains parallel to the a axis

Metathesis of Fatty Acid Ester Derivatives in 1,1-Dialkyl and 1,2,3-Trialkyl Imidazolium Type Ionic Liquids

The self-metathesis of methyl oleate and methyl ricinoleate was carried out in the presence of ruthenium alkylidene catalysts 1–4 in [bmim] and [bdmim][X] type ionic liquids (RTILs) (X = PF6−, BF4− and NTf2−) using the gas chromatographic technique. Best catalytic performance was obtained in [bdmim][X] type ionic liquids when compared with [bmim][X] type ionic liquids. Catalyst recycling studies were also carried out in the room temperature ionic liquids (RTILs) with catalysts 1–4 in order to explore their possible industrial application

Catalytic transfer hydrogenation in γ-valerolactone-based ionic liquids

The combination of transfer hydrogenation reaction with the advantages of γ-valerolactone-based ionic liquids could result in an environmentally benign method for the reduction of organic substrates. Ionic liquids containing 4-hydroxyvalerate anion were applied as alternative solvents for the reduction of acetophenone, its substituted forms and different alkenes using transition metal based catalysts. The optimal conditions (e.g. type of catalyst precursor and hydrogen donor) for the transformation were also specified

Synthesis and characterisation of novel nopyl-derived phosphonium ionic liquids

A series of novel nopyl-derived chiral phosphonium ionic liquids have been successfully synthesised and characterised. Analysis of each novel ionic liquid was conducted in order to confirm structure, purity and thermal stability

Directly probing the effect of the solvent on a catalyst electronic environment using X-ray photoelectron spectroscopy

The electronic environment of the metal centre of a catalyst dissolved in ionic liquids has a determining effect on its catalytic efficiency in chemical reactions. However, the electronic environment of the ionic liquid-based metal centres can be influenced by not only their chemical state but also the solute–solvent interaction. In this work, we demonstrate that the anion of an ionic liquid can significantly influence the electronic environment of a metal centre. The metal centre electronic environment can be monitored by measuring the typical electron binding energies by X-ray photoelectron spectroscopy (XPS). The correlation of the electronic environment of the metal centre with reaction performance provides a possibility to design and control a chemical reaction. In this work, we also illustrate a strategy for tuning the electronic environment of metal centres, by the selection of particular ionic liquid anions, to design a catalytic system and consequently to finally control the reaction performance of a model Suzuki cross coupling reaction

Isoconversional kinetic analysis applied to five phosphoniumcation-based ionic liquids

Thermal degradation of five phosphonium cation-based ionic liquids ([P66614][BEHP], [P66614][(iC8)2PO2],[P66614][NTf2], [P44414][DBS] and [P4442][DEP]) was studied using dynamic methodology (25–600◦C at 5,10 and 20◦C/min) in both inert (nitrogen) and reactive (oxygen) atmospheres. In addition, isothermalexperiments (90 min at 200, 225 and 250◦C) were carried out with [P66614][(iC8)2PO2]. Results indicatethat thermal stability is clearly dominated by the coordination ability of the anion, with [P66614][NTf2] out-performing the other ones in both pyrolytic and oxidising conditions. Although the thermal degradationmechanism is affected by atmospheric conditions, the degradation trend remains practically constant.As the dynamic methodology usually overestimates the long-term thermal stability, an isoconversionalmethodology is better for predicting the long-term thermal stability of these ionic liquids in order to beused as base oil or additive in lubricants formulation. Finally, the model-free methodology can predict atlower costs the ILs performance in isothermal conditions

Revisiting Heck-Mizoroki reactions in ionic liquids

The use of ionic liquids as an alternative to conventional organic solvents has been an important research topic in order to answer economic and environmental challenges. This critical review revisits the different approaches and achievements on the use of ionic liquids as solvents in Heck-Mizoroki coupling reactions; a brief reference to supported ionic liquids will be also highlighted