Cluster ionic liquids

In pyridinium chloride ionic liquids and in l,2-dimethyl-3-hexylimida2olium chloride ([HMMIMjCl), where the C(2) position is protected by a methyl group, only [PdClJ was observed, whereas in [HMIMjCl, the EXAFS showed the formation of a bis-carbene complex. In the presence of triphenylphosphine, Pd-P coordination was observed in all ionic liquids except where the carbene complex was formed. During the Heck reaction, the formation of palladium was found to be quicker than in the absence of reagents. Overall, the EXAFS showed the presence of small palladium clusters of approximately 1 nm diameter formed in solution. 

Much emphasis has been placed in recent times on easily recoverable liquid bi-phasic catalysts, including metal clusters in nonconventional solvents. For instance, aqueous solutions of the complexes [Ru3(CO)12.x(TPPTS)x] (x=l, 2, 3 TPPTS = triphenylphosphine-trisulfonate, P(m-C6H4S03Na)3) catalyze the hydrogenation of simple alkenes (1-octene, cyclohexene, styrene) at 60°C and 60 bar H2 at TOF up to 500 h 1 [24], while [Ru i(CO)C (TPPMS) >,] (TPPMS = triphenylphos-phine-monosulfonate, PPh2(m-C6H4S03Na) is an efficient catalyst precursor for the aqueous hydrogenation of the C=C bond of acrylic acid (TOF 780 h 1 at 40 °C and 3 bar H2) and other activated alkenes [25]. The same catalysts proved to be poorly active in room temperature ionic liquids such as [bmim][BF4] (bmim= Tbutyl-3-methylimidazolium). No details about the active species involved are known at this point. 

Carbon yields, 72 274 Carbonylation, 73 654-656 ionic liquids in, 26 882-885 methanol, 76 315 of methyl acetylene, 7 6 245 reaction, 70 506-507 Carbonyl bromide, 4 300 Carbonyl clusters, high nuclearity, 76 64-66... 

Transition-metal carbonyls, 16 58 Transition metal catalysts, 20 151-152 Transition-metal-catalyzed microwave-assisted reactions, 16 552 Transition metal-catalyzed reactions in ionic liquids, 26 878-897 Transition-metal clusters, structure of,... 

Whole-cell biocatalysts, organic solvents and, 16 412-413 Whole cells, 3 669-671 Whole-cell systems ionic liquids in, 26 897 Whole cluster pressing in white wine, 26 311 Whole-wheat flour, 26 279, 283 Whole yeast vaccines, 26 488 Who needs it concept, 24 190 Wicking limit, heat pipe, 13 230 Wicks... 

The dicationic cluster catalyst H4Ru4(r/ -C6H6) [BF4]2, originally developed for biphasic aqueous-organic arene hydrogenation reactions (see Section 8.2.1), has proven to be more effective in ionic liquids presumably due to increased... 

It is also remarkable that the rhodium complex catalyst in the supported ionic liquid showed long-term stability, being used for 18 batches without any significant loss of activity. It was confirmed that no rhodium metal clusters were formed. However, acetone could be used to remove the ionic layer and its presence led to a total loss of activity. 

Analysis of supramolecular structures in ionic liquids Supramolecular assemblies are the molecular base for some of the unique properties of ILs. Therefore, the knowledge of the nature, type, and strength of these structures [23] is a prerequisite for a deeper understanding of ILs as well as for the tailor-made design of new compounds. The most important noncovalent interactions responsible for the formation of such a structure are C-H hydrogen bonds [25]. Other interactions encompass the formation of clusters by ion pairing, which can be found, for example, in chloroaluminates [12]. 

Attempts have also been made to develop biphasic methodologies for the hydrogenation of aromatics. The hydrogenation of benzene derivatives was studied using various Ru complexes.468,469 A trinuclear cluster cationic species was isolated as the tetrafluoroborate salt and showed increased activity in hydrogenation.470 The air/ moisture-stable [bmim][BF4] ionic liquid and water with [Rh r -CgHg).,] [BF4] as the catalyst precursor is an effective system under usual conditions (90°C, 60 atm)471 A system composed of stabilized Rh(0) nanoparticles proved to be an efficient catalyst in the hydrogenation of alkylbenzenes 472... 

Fluorinated ionic liquids, characteristics, 1, 854 Fluorinated molecules, coordination, 1, 727 Fluorinated thiols, in nanoparticle preparation, 12, 80 Fluorination, and iridium carbonyl cluster complexes, 7, 299... 

Excision reactions are sometimes accompanied by redox chemistry. For example, dissolution of the 2D solid Na4Zr6BeCli6 in acetonitrile in the presence of an alkylammonium chloride salt results in simultaneous reduction of the cluster cores (144). Here, the oxidation product remains unidentified, but is presumably the solvent itself. As a means of preventing such redox activity, Hughbanks (6) developed the use of some room temperature molten salts as excision media, specifically with application to centered zirconium-halide cluster phases. A number of these solids have been shown to dissolve in l-ethyl-2-methylimidazolium chloride-aluminum chloride ionic liquids, providing an efficient route to molecular clusters with a full compliments of terminal chloride ligands. Such molten salts are also well suited for electrochemical studies. 

---