Ionic liquids: polar, but weakly coordinating solvents for the first biphasic oligomerisation of ethene to higher α-olefins with cationic Ni complexes

Wasserscheid, Peter; Gordon, Christopher P.; Hilgers, Claus; Muldoon, Mark J.; Dunkin, Ian R.

doi:10.1039/b101400p

Cited by 181 publications

(109 citation statements)

References 15 publications

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“…Very little solubility data for alkene substrates in ionic liquids are available at present in the literature, [35][36][37] and therefore the solubility of 1-octene in ionic liquids was determined by gas chromatography (see Supporting Information). For ionic liquids based on the same cation the solubility increases the order…”

Section: Solubility Of 1-octene In Ionic Liquidsmentioning

confidence: 99%

Metathesis of 1‐Octene in Ionic Liquids and Other Solvents: Effects of Substrate Solubility, Solvent Polarity and Impurities

et al. 2006

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Abstract:With the self-metathesis of 1-octene to 7-tetradecene catalyzed by Grubbs 1 st generation [benzylidene-bis(tricyclohexylphosphine)dichlororuthenium, (1)] precursor at low concentrations (0.02 mol %) as basis, the effects of the solubility of the substrate in ionic liquids, the solvent polarity, as well as the influence of various impurities stemming from the preparation of ionic liquids have been investigated. The solubility of the substrate in the ionic liquid has little effect on the conversion, and the reaction is not mass-transfer limited. While a higher polarity of an organic solvent increases the rate, it is independent of the polarity excerted by the cation of an ionic liquid. Of paramount importance for reproducible results is the purity of ionic liquids. An extensive study shows that catalyst deactivation by impurities increases in the order of water < halide < 1-methylimidazole. In the presence of water or 1-methylimidazole impurities, the Grubbs-Hoveyda precursor (3) is superior to both the 1 st (1) and 2 nd (2) generation Grubbs complexes. Under impurity-free conditions or in the presence of chloride, the performance of 2 is equivalent to that of 3.

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Section: Solubility Of 1-octene In Ionic Liquidsmentioning

confidence: 99%

Metathesis of 1‐Octene in Ionic Liquids and Other Solvents: Effects of Substrate Solubility, Solvent Polarity and Impurities

et al. 2006

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“…This degree of coordination has been correlated to solvent effect observed in Ni catalysed oligomerisation of ethylene. 138 Apart from the properties already discussed, the ionic liquids are non-flammable materials. The nonflammable liquids with high ionic conductivity and inherent non-volatility are practical materials for use in electrochemistry.…”

Section: Inorganic Synthesis In Ionic Liquidsmentioning

confidence: 99%

Electrochemical routes for industrial synthesis

Sequeira¹,

Santos²

2009

J. Braz. Chem. Soc.

118

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Esta revisão examina as razões que justificam um interesse crescente da indústria química pelos processos eletrolíticos. Reveem-se as indústrias químicas, nas quais compostos orgânicos e inorgânicos são processados e descrevem-se os avanços tecnológicos mais relevantes. Inicialmente, abordam-se processos bem estabelecidos, como as indústrias cloroalcalinas de produção de alumínio, p-aminofenol, adiponitrila, etileno glicol, antraquinona, produtos perfluorados, ácido glioxílico e L-cisteína. Face à grande quantidade de informação disponível, o assunto é tratado com base científica, mas de modo bastante simplificado. Posteriormente, descrevem-se processos orgânicos e inorgânicos emergentes, nomeadamente processos eletroquímicos mediados e síntese em líquidos iónicos. Estabelecem-se paralelos entre síntese química e síntese eletroquímica. Estimula-se o interesse nos processos de eletrossíntese, particularmente em líquidos iónicos, não desmerecendo a importância das vias puramente químicas de síntese orgânica e inorgânica.This review examines the reasons for increasing interest towards electrolyses by the chemical industry, reviews the electrochemical industries as most of them now exist, and provides a status report on the key technological advances which are occurring to meet present and future needs. Classical industries like those of chloroalkali, aluminium, p-aminophenol, adiponitrile, ethylene glycol, anthraquinone, perfluorinated products, glyoxylic acid and L-cysteine are initially covered. Considering the large amount of available publications in these topics of electrochemical engineering, the covered relevant information is treated at a scientific level, although in a simplified way. Then the paper deals with emerging inorganic and organic processes, e.g. electrosynthesis in ionic liquids and mediated electrochemical processes, and finishes by assessing what the future development trend might be given the electrochemical and non electrochemical competing influences. With this approach it is hoped to stimulate the interest of chemical engineers and scientists non-specialised in electrochemical routes, and to review some cutting edge research, particularly as far as electrosynthesis in ionic liquids is concerned.

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“…Our group reported on the structural characterization of VO(acac) 2 in imidazolium ionic liquids, and showed that the vanadium complex is solvatochromic in the selected ionic liquids and behaves as in organic solvents, evidencing coordination of the ionic liquid anion in the solvents with higher coordinating ability. 9 The Lewis basicity order obtained in this study was: PF 6 -< NTf 2 -< OTf In this paper we take our studies further and investigate the effect of the solvent on the Visible and EPR parameters of mixed cationic complexes containing acetylacetonate and aromatic diimines.…”

Section: Introductionmentioning

confidence: 99%

“…2,3 Many techniques have been used to study the coordination ability of the ionic liquid anion, the simplest one being the measurement of the Vis spectra of solvatochromic dyes.…”

Section: Introductionmentioning

confidence: 99%

“…Particularly, the following transition metal complexes have been used as solvatochromic probes: [Fe(phen) 2 4 ] the visible electronic absorption bands can be correlated with solvent donor numbers. 8 A shift in the lowest energy band (in the Vis range) is observed and is a result of the d-orbital splitting of copper(II) when the complex becomes penta-or hexa-coordinated.…”

Section: Introductionmentioning

confidence: 99%

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The solvation and redox behavior of mixed ligand copper(II) complexes of acetylacetonate and aromatic diimines in ionic liquids

Nunes

Nagy

Alegria

et al. 2014

Inorganica Chimica Acta

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The behavior of two cationic copper complexes of acetylacetonate and 2,2'-bipyridine or 1,10-phenanthroline, Cu(acac)(bipy)Cl (1) and Cu(acac)(phen)Cl (2), in organic solvents and ionic liquids, was studied by spectroscopic and electrochemical techniques. Both complexes showed solvatochromism in ionic liquids although no correlation with solvent parameters could be obtained. By EPR spectroscopy rhombic spectra with well-resolved superhyperfine structure were obtained in most ionic liquids. The spin Hamiltonian parameters suggest a square planar geometry with coordination of the ionic liquid anion. The redox properties of the complexes were investigated by cyclic voltammetry at a Pt electrode (d = 1 mm) in bmimBF 4 and bmimNTf 2 ionic liquids and showed that complexes 1 and 2 can be electrochemically reduced in these ionic media. The results show that both copper (II) complexes are reduced at more negative potentials when cyclic voltammetries are conducted in ionic liquids instead of organic solvents, thus being more difficult to reduce in these ionic solvents. This is in agreement with the EPR characterization, which shows lower A z and higher g z values for the complexes dissolved in ionic liquids, than in organic solvents, due to higher electron density at the Copper center.The anion basicity order obtained by EPR is NTf 2  , N(CN) 2  , MeSO 4  and Me 2 PO 4  , which agrees with previous determinations.

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Ionic liquids: polar, but weakly coordinating solvents for the first biphasic oligomerisation of ethene to higher α-olefins with cationic Ni complexes

Cited by 181 publications

References 15 publications

Metathesis of 1‐Octene in Ionic Liquids and Other Solvents: Effects of Substrate Solubility, Solvent Polarity and Impurities

Metathesis of 1‐Octene in Ionic Liquids and Other Solvents: Effects of Substrate Solubility, Solvent Polarity and Impurities

Electrochemical routes for industrial synthesis

The solvation and redox behavior of mixed ligand copper(II) complexes of acetylacetonate and aromatic diimines in ionic liquids

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