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Relevant academic research and scientific papers

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

Air-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.

A fast-initiating ionically tagged ruthenium complex: A robust supported pre-catalyst for batch-process and continuous-flow olefin metathesis

In this study, a new pyridinium-tagged Ru complex was designed and anchored onto sulfonated silica, thereby forming a robust and highly active supported olefin-metathesis pre-catalyst for applications under batch and continuous-flow conditions. The involvement of an oxazine-benzylidene ligand allowed the reactivity of the formed Ru pre-catalyst to be efficiently controlled through both steric and electronic activation. The oxazine scaffold facilitated the introduction of the pyridinium tag, thereby affording the corresponding cationic pre-catalyst in good yield. Excellent activities in ring-closing (RCM), cross (CM), and enyne metathesis were observed with only 0.5mol % loading of the pre-catalyst. When this powerful pre-catalyst was immobilized onto a silica-based cationic-exchange resin, a versatile catalytically active material for batch reactions was generated that also served as fixed-bed material for flow reactors. This system could be reused at 1mol % loading to afford metathesis products in high purity with very low ruthenium contamination under batch conditions (below 5ppm). Scavenging procedures for both batch and flow processes were conducted, which led to a lowering of the ruthenium content to as little as one tenth of the original values. Tag! You're it! A pyridinium-tagged Ru complex (see figure) that was anchored to sulfonated silica formed a robust and highly active supported olefin-metathesis pre-catalyst for applications under batch and continuous-flow conditions with low ruthenium leaching.

Effect of ligand bulk in ruthenium-catalyzed olefin metathesis: IPr* vs IPr

Novel ruthenium catalysts, [RuCl2(IPr*)(PPh 3)(3-phenylindenylidene)] (1) and [RuCl2(IPr*)(Py) (3-phenylindenylidene)] (2), bearing the very bulky ligand IPr* are reported. The complexes were tested in ring closing and cross-metathesis, and their activities were compared to that displayed by [RuCl2(IPr) (PPh3)(3-phenylindenylidene)] (3) and the new [RuCl 2(IPr)(Py)(3-phenylindenylidene)] (4), in order to assess how the steric hindrance of the N-heterocyclic carbene influences the catalytic activity of the resulting ruthenium complexes.

The influence of phosphane ligands on the versatility of ruthenium-indenylidene complexes in metathesis

The aim of the present study is to develop readily available and stable pre-catalysts that could be easily prepared on large scale from simple starting materials. Based on the hypothesis that substitution of classical PCy3 with phosphanes of varying elect

Backbone tuning in indenylidene-ruthenium complexes bearing an unsaturated N-heterocyclic carbene

The steric and electronic influence of backbone substitution in IMes-based (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2- ylidene) N-heterocyclic carbenes (NHC) was probed by synthesizing the [RhCl(CO)2(NHC)] series of complexes to quantify

Halide exchanged Hoveyda-type complexes in olefin metathesis

The aims of this contribution are to present a straightforward synthesis of 2nd generation Hoveyda-type olefin metathesis catalysts bearing bromo and iodo ligands, and to disclose the subtle influence of the different anionic co-ligands on the catalytic performance of the complexes in ring opening metathesis polymerisation, ring closing metathesis, enyne cycloisomerisation and cross metathesis reactions.

New efficient ruthenium metathesis catalyst containing chromenyl ligand

A synthesis of new Hoveyda-Grubbs-type catalyst with chromenyl ligand was described herein. The new catalyst was tested in model RCM and CM reactions. The catalyst proved to be quite efficient. It showed activity comparable or superior to that of commercially available Grubbs second-generation complexes.

New library of aminosulfonyl-tagged Hoveyda-Grubbs type complexes: Synthesis, kinetic studies and activity in olefin metathesis transformations

Seven novel Hoveyda-Grabbs precatalysts bearing an aminosulfonyl function are reported. Kinetic studies indicate an activity enhancement compared to Hoveyda's precatalyst. A selection of these catalysts was investigated with various substrates in ring-clo