Chlorostannate ionic liquids

The ability of iron(III) chloride genuinely to catalyze Friedel-Crafts acylation reactions has also been recognized by Holderich and co-workers [97]. By immobilizing the ionic liquid [BMIM]Cl/FeCl3 on a solid support, Holderich was able to acetylate mesitylene, anisole, and m-xylene with acetyl chloride in excellent yield. The performance of the iron-based ionic liquid was then compared with that of the corresponding chlorostannate(II) and chloroaluminate(III) ionic liquids. The results are given in Scheme 5.1-67 and Table 5.1-5. As can be seen, the iron catalyst gave superior results to the aluminium- or tin-based catalysts. The reactions were also carried out in the gas phase at between 200 and 300 °C. The acetylation reac-... 

Ionic liquids formed by treatment of a halide salt with a Lewis acid (such as chloro-aluminate or chlorostannate melts) generally act both as solvent and as co-catalyst in transition metal catalysis. The reason for this is that the Lewis acidity or basicity, which is always present (at least latently), results in strong interactions with the catalyst complex. In many cases, the Lewis acidity of an ionic liquid is used to convert the neutral catalyst precursor into the corresponding cationic active form. The activation of Cp2TiCl2 [26] and (ligand)2NiCl2 [27] in acidic chloroaluminate melts and the activation of (PR3)2PtCl2 in chlorostannate melts [28] are examples of this land of activation (Eqs. 5.2-1, 5.2-2, and 5.2-3). 

As early as 1972 Parshall described the platinum-catalyzed hydroformylation of ethene in tetraethylammonium trichlorostannate melts [1]. [NEt4][SnCl3], the ionic liquid used for these investigations, has a melting point of 78 °C. Recently, platinum-catalyzed hydroformylation in the room-temperature chlorostannate ionic liquid [BMIM]Cl/SnCl2 was studied in the author s group. The hydroformylation of 1-octene was carried out with remarkable n/iso selectivities (Scheme 5.2-13) [66]. 

Despite the limited solubility of 1-octene in the ionic catalyst phase, a remarkable activity of the platinum catalyst was achieved [turnover frequency (TOP) = 126 h ]. However, the system has to be carefully optimized to avoid significant formation of hydrogenated by-product. Detailed studies to identify the best reaction conditions revealed that, in the chlorostannate ionic liquid [BMIM]Cl/SnCl2 [X(SnCl2) = 0.55],... 

Moreover, these experiments reveal some unique properties of the chlorostan-nate ionic liquids. In contrast to other known ionic liquids, the chlorostannate system combine a certain Lewis acidity with high compatibility to functional groups. The first resulted, in the hydroformylation of 1-octene, in the activation of (PPli3)2PtCl2 by a Lewis acid-base reaction with the acidic ionic liquid medium. The high compatibility to functional groups was demonstrated by the catalytic reaction in the presence of CO and hydroformylation products. 

Chlorostannate ionic liquids have been used in hydroformylation reactions [23], Acidic [bmimjCl-SnCb and [l-butyl-4-methylpyridinium]Cl-SnCl2 were prepared from mixing the respective [cation]+ Cl with tin(II)chloride in a ratio of 100 104, much in the same way that the chloroaluminates are made (see Chapter 4). Both these chlorostannate ionic liquids melt below 25 °C. Addition of Pd(PPh3)2Cl2 to these chlorostannate ionic liquids leads to a reaction medium that catalyses the hydroformylation of alkenes such as methyl-3-pentenoate as shown in Scheme 8.9. The ionic liquid-palladium catalyst solution is more effective than the corresponding homogeneous dichloromethane-palladium catalyst solution. The product was readily separated from the ionic liquid by distillation under vacuum. This is an important reaction as it provides a clean route to adipic acid. 

Ionic liquids formed by the reaction of a halide salt with a Lewis acid (e.g. chloroa-luminate or chlorostannate melts) generally act as both solvent and co-catalyst in... 

The same authors also studied the kinetics of [(PPh3)2PtCl2] activation in chlorostan-nate ionic liquids by UV-Vis spectroscopy [73]. Apart from investigations in neat chlorostannate melts they also investigated the activation in [BMIM][(CF3S02)2N] after addition of [BMIM]Q/SnQ2 (equimolar composition in tenfold excess to the added Pt(ii)-complex). The observed reaction was found to proceed in two steps. 

Later, van Eldik et al. studied in more detail the kinetics of the formation of the active hydroformylation catalysts ds-[Pt(PPh3)2Cl(SnCl3)] and cis-[Pt(PPh3)2(SnCl3)2] from the precursor ds-[Pt(PPh3)202] in the presence of SnCl2 in different imidazolium-based chlorostannate ionic liquids (for analytic details see Section 5.3.1.3) [73]. 

Carbonate Catalyzed with Ionic Liquids Imidazolium Chloroaluminate and Chlorostannate Melts." Maerotnoleeular Rapid Commun, 23, 757-760. 

Currie, M., Estager, J., Licence, R, Men, S., Nockemann, R, Seddon, K.R., Swadzba-Kwasny, M. and Terrade, C., Chlorostannate(ll) ionic liquids Speciation, Lewis acidity, and oxidative stability, Inorg. Chem. 52 (4), 1710-1721 (2013). 

The regioselective hydroformylation of functionalized and nonfunctionalized olefins can also be performed by platinum compounds [26] in chlorostannate ionic liquids as solvents for homogeneous catalysis (entries 20-22, Table 6.1). Dissolved in chlorostannate ionic liquids, the Pt catalyst shows enhanced stability and selectivity in the hydroformylation of methyl-3-pentenoate compared to the identical reaction in conventional organic solvents. The moderate Lewis acidity of these ionic liquids allows the activation of the Pt catalyst combined with tolerance of the functional groups in the substrate. In the case of 1-octene hydroformylation, a biphasic reaction system could be performed using the chlorostannate ionic liquid. 

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