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International audience; Brought to life more than half a century ago and successfully applied for high-value petrochemical intermediates production, nickel-catalyzed olefin oligomerization is still a very dynamic topic, with many fundamental questions to address and industrial challenges to overcome. The unique and versatile reactivity of nickel enables the oligomerization of ethylene, propylene and butenes into a wide range of oligomers that are highly sought-after in numerous fields to be controlled. Interestingly, both homogeneous and heterogeneous nickel catalysts have been scrutinized and employed to do this. This rare specificity encouraged us to interlink them in this review so as to open up opportunities for further catalyst development and innovation. An in-depth understanding of the reaction mechanisms in play is essential to being able to fine-tune the selectivity and achieve efficiency in the rational design of novel catalytic systems. This review thus provides a complete overview of the subject, compiling the main fundamental/industrial milestones and remaining challenges facing homogeneous/heterogeneous approaches as well as emerging catalytic concepts, with a focus on the last 10 years.

International audience; The reactivity of a phenoxy-imine-ether system (FI)TiCl3/MAO was studied toward selective ethylene trimerization. This system was shown to either trimerize or polymerize ethylene depending on the reaction temperature. Its selectivity switches from a significant production of the trimerization product, 1-hexene (85 wt %, 520-450 kg1-hexene gTi-1 h-1) between 30 and 40 °C, to a moderate polyethylene formation (70-80 wt %, 60-70 kgpolyethylene gTi-1 h-1) at higher reaction temperature (T > 60 °C). Polymerization was investigated based on an original "polymer-to-catalyst" strategy aiming at identifying the active species responsible for this side reaction. Using DSC, SEC and high temperature 13 C NMR analyses, polyethylenes were found to exhibit high molar masses (> 10 5 g mol-1) and a low 1-hexene content (< 1 mol %) at any temperature. Kinetic studies support that trimerization and polymerization species are generated from the catalyst precursor at 40 °C but a parallel process may occur at higher temperature. The increase dispersity to 4.6 at 80 °C suggests a change from single to multisite catalysis. The poor comonomer incorporation ability of the active species is reminiscent of a molecular Ziegler Natta or a bulky postmetallocene catalyst.

This work presents the epoxidation of camphene employing methyltrioxorhenium(VII) (MTO) as catalyst. The effect of different factors on the formation of camphene oxide with respect to high yield and selectivity was investigated. First, the ratio camphene:MTO:pyrazole:H2O2 was studied in dichloromethane as solvent in order to determine the optimal condition. Moreover, the influence of the Lewis base adduct (tert-butylpyridine, 4,4'-dimethy1-2,2'-bypridine, imidazole or pyrazole) was investigated. The effect of an aqueous oxidant, namely H2O2 and a solid oxidant, namely urea hydrogen peroxide (UHP) was also examined. Finally, the solvent was varied from dichloromethane to chloroform, toluene and nitromethane. Based on the results the optimal conditions for the epoxidation of camphene using MTO as catalyst were determined. The molar ratio camphene:MTO:pyrazole: H2O2 of 100:0.5:10:110 in dichloromethane at room temperature leads after 3 h to 97

This report presents a study of the epoxidation of limonene employing methyltrioxorhenium (MTO) as catalyst. The influence of base ligands, namely t-butylpyridine, 4,4′-dimethyl-2,2′-bipyridine and pyrazole on the catalytic activity was investigated. The choice of the oxidant (H2O2 in water or H2O2 stabilized by urea) was also examined. The effect of the solvent has been studied in order to determine optimal conditions for the epoxidation of (+)-limonene. The best result was obtained when a molar ratio (+)-limonene:MTO:H2O2:t-butylpyridine of 100:0.5:10:150 was used at 25 °C in dichloromethane. 1,2-Limonene oxide was formed with 77% yield and 96% selectivity after 1 h with a TOF of ca. 900 h−1.

The epoxidation of α-pinene employing methyltrioxorhenium as catalyst is examined. The influence of mono- and bidentate Lewis basic additives (e.g. tbutylpyridine, 4,4′-dimethyl-2,2′-bipyridine, and Schiff-bases) is investigated. Additionally the impact of the oxidant (H2O2 in water or urea–hydrogen peroxide (UHP)) on the catalytic performance is studied. The effect of the solvent is also examined in order to determine the optimal conditions for the epoxidation of α-pinene. The best and straightforwardly applicable result is obtained when a ratio α-pinene:MTO:tbutylpyridine:UHP of 200:1:40:600 is applied at 0 °C in nitromethane. In this case, α-pinene oxide is formed with 95% yield after 3 h with a turnover frequency (TOF) of 610 h−1.