and Perspectives Sophie Carenco,†,‡,§,∥,⊥ David Portehault,*,†,‡,§ Ced́ric Boissier̀e,†,‡,§ Nicolas Meźailles, and Cleḿent Sanchez*,†,‡,§ †Chimie de la Matier̀e Condenseé de Paris, UPMC Univ Paris 06, UMR 7574, Colleg̀e de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France ‡Chimie de la Matier̀e Condenseé de Paris, CNRS, UMR 77574, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Chimie de la Matier̀e Condenseé de Paris, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Laboratory Heteroelements and Coordination, Chemistry Department, Ecole Polytechnique, CNRS-UMR 7653, Palaiseau, France

Nanoscaled metal borides and phosphides: recent developments and perspectives

Over the last few years, ionic liquids have successfully been applied as alternative solvents for homogeneous biphasic catalysis. 1-5 Many transition metal complexes dissolve readily in ionic liquids, which enables their use as solvents for transition metal catalysis. Sufficient solubility for a wide range of catalyst complexes is an obvious, but not trivial, prerequisite for a versatile solvent for homogeneous catalysis. Obviously, there are many other good reasons to apply ionic liquids as alternative solvents in transition metal-catalyzed reactions. Besides their very low vapor pressure and their good thermal stability, an important advantage is the possibility to tune their solubility and acidity/coordination properties by varying the nature of the anions and cations systematically. 6 The possibility of adjusting solubility properties is of particular importance for liquid -liquid biphasic catalysis. Liquid-liquid catalysis can be realized when one liquid is able to dissolve the catalyst and displays a partial solubility with the substrates and a poor solubility with the reaction products. Under these conditions, the product phase, containing also the unconverted reactants, is removed by simple phase decantation and the liquid containing the catalyst can be recycled. In hydroformylation, this concept has been successfully applied for reactions of short alkenes in the Ruhrchemie/Rho ˆne-Poulenc Process (RCH/RP). 7-9

Hydroformylation in room temperature ionic liquids (RTILs): catalyst and process developments.

Amorphous alloys structurally deviate from crystalline materials in that they possess unique short-range ordered and long-range disordered atomic arrangement. They are important catalytic materials due to their unique chemical and structural properties including broadly adjustable composition, structural homogeneity, and high concentration of coordinatively unsaturated sites. As chemically reduced metal–metalloid amorphous alloys exhibit excellent catalytic performance in applications such as efficient chemical production, energy conversion, and environmental remediation, there is an intense surge in interest in using them as catalytic materials. This critical review summarizes the progress in the study of the metal–metalloid amorphous alloy catalysts, mainly in recent decades, with special focus on their synthetic strategies and catalytic applications in petrochemical, fine chemical, energy, and environmental relevant reactions. The review is intended to be a valuable resource to researchers interested in these exciting catalytic materials. We concluded the review with some perspectives on the challenges and opportunities about the future developments of metal–metalloid amorphous alloy catalysts.

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Synthesis and catalysis of chemically reduced metal–metalloid amorphous alloys

An economically meaningful hydroformylation of long-chain olefins requires an efficient combination of both a high-yield reaction step and efficient catalyst recycling. The application of thermomor...

Hydroformylation of 1-Dodecene in the Thermomorphic Solvent System Dimethylformamide/Decane. Phase Behavior–Reaction Performance–Catalyst Recycling

Peroxymonosulfate activation by Co9S8@ S and N co‐doped biochar for sulfamethoxazole degradation

Selective hydrogenation of benzene to cyclohexene over RuCoB/γ-Al2O3 without additive

Metal-promoted hydrolysis of bis(p-nitrophenyl)phosphate by trivalent manganese complexes with Schiff base ligands in Gemini micellar solution

The preparation of a new surface-active sulfonated phosphine and its catalytic performance in aqueous biphasic hydroformylation of long chain olefins were reported. The amphiphilic phosphine: sodium salt of sulfonated n-C12H25O C6H4P(C6H4-p-CH3O)2 (DMOPPS) was prepared by sulfonation of the hydrophobic phosphine DMOPP in concentrated H2SO4 under N2 atmosphere at 30 °C for about 5 h. The rhodium complex, RhCl(CO)(TPPTS)2 [TPPTS =P(C6H4-m-SO3Na)3], was used as the catalyst precursor. The catalytic active species with the DMOPPS as ligand was in situ formed by adding DMOPPS to the RhCl(CO)(TPPTS)2 catalyst precursor. The surface-activity and micelle-forming property of this new amphiphilic phosphine were confirmed by using cryogenic transmission electron microscope (Cryo-TEM). Under the same conditions, the biphasic hydroformylation of 1-decene using DMOPPS as ligand was compared with that using traditional TPPTS as ligand. The catalysis system using DMOPPS was also compared with the previous Rh-TPPTS-surfactant [C12H25N(CH3)3I (DTAI)] system. Some reaction parameters such as stirring rates, alkyl chain length of olefins, the molar ratio of phosphine/rhodium, and the catalyst recycle were also studied in detail. The results showed that the ligand DMOPPS exhibited a micelle-forming property that could significantly enhance the hydroformylation reaction rate of long chain olefin. Moreover, the surface-active phosphine may also stabilize the aqueous/oil phase boundary, which could enhance the biphasic catalytic reaction rates.

Application of a new amphiphilic phosphine in the aqueous biphasic catalytic hydroformylation of long chain olefins

Cleavage of phosphate diesters mediated by Zn(II) complex in Gemini surfactant micelles.

The biphasic hydroformylation of higher olefins was performed efficiently in the halogen-free ionic liquids 1- n -alkyl-3-methylimidazolium p -toluenesulfonate ([Rmim][ p- CH 3 C 6 H 4 SO 3 ]) using Rh-TPPTS [TPPTS: trisodium salt of tri( m -sulphonylphenyl)phosphine] complexes as catalyst. The catalytic system offers high activity and chemoselectivity for aldehyde with a good retention of the catalyst in ionic liquid phase. The ionic liquid containing catalyst can be easily separated and reused several times without a significant decrease in the activity and selectivity. The results indicated that the cation and anion of ionic liquids strongly influenced the reaction rate. Furthermore, the reaction rate was markedly accelerated when the chain-length of alkyl in ionic liquids was comparable with that of olefin. A “matching effect” between the chain-length of alkyl in ionic liquids and that of olefins was firstly reported.

Weidong Jiang

Papers

Selective hydrogenation of benzene to cyclohexene over RuCoB/γ-Al2O3 without additive

Metal-promoted hydrolysis of bis(p-nitrophenyl)phosphate by trivalent manganese complexes with Schiff base ligands in Gemini micellar solution

Application of a new amphiphilic phosphine in the aqueous biphasic catalytic hydroformylation of long chain olefins

Cleavage of phosphate diesters mediated by Zn(II) complex in Gemini surfactant micelles.

Hydroformylation of higher olefin in halogen-free ionic liquids catalyzed by water-soluble rhodium–phosphine complexes