Trisulfonate ligands

This Chapter will concentrate on the hydroformylation of propene by means of rhodium catalysts, modified by water-soluble ligands such as TPPTS (triphenylphosphine m-trisulfonate). 

Typical approaches to this biphasic system have involved the immobilization of catalysts in the aqueous phase as colloids [53] or using water-soluble catalysts based on ligands such as the trisulfonated TPPTS [55, 56]. Particularly high reaction rates have been obtained with surfactant-stabilized microemulsions and emulsions that allow for intimate contact of all reagents with the catalyst during the reaction [57]. The emulsions separate readily into two phases by small pressure changes and the C02-phase is then vented to isolate the products. The catalyst RhCl(tppds)3 (tppds =... 

In order to keep the mild conditions, hydroxycarbonylation has been performed in biphasic media, maintaining the catalyst in the aqueous phase thanks to water-soluble mono- or diphosphine ligands. In the presence of the sodium salt of trisulfonated triphenylphosphine (TPPTS), palladium was shown to carbonylate efficiently acrylic ester [19], propene and light alkenes [20,21] in acidic media. For heavy alkenes the reduced activity due to the mass transfer problems between the aqueous and organic phases can be overcome by introducing an inverse phase transfer agent, and particularly dimeihyl-/-i-cyclodextrin [22,23]. Moreover, a dicationic palladium center coordinated by the bidentate diphosphine ligand 2,7-bis(sulfonato)xantphos (Fig. 2) catalyzes, in the presence of tolylsulfonic acid for stability reasons, the hydroxycarbonylation of ethylene, propene and styrene and provides a ca. 0.34 0.66 molar ratio for the two linear and branched acids [24],... 

To avoid difficulties with the low solubility of Pd/TPPTS the monosul-fonated triphenylphosphine (TPPMS) was used as the ligand, which is less polar than the trisulfonated TPPTS. With the following solvents s3 a homogeneous phase is obtained DMF, DMSO, PEG 400 and isopropyl alcohol. A smaller amount of the mediator is required if TPPMS is used than with TPPTS as the hgand. hi further experiments the use of polyethylene glycol... 

Interestingly, when a water-soluble bisphosphine, a 86/14 mixture of tetra- and trisulfonated l,3-bis(diphenylphosphino)propane was used as ligand, the rate of carbonylation did not change considerably, however, the selectivity to Ibuprofen was only 22 % and the major product was 3-IPPA (78 %). 

Replacement of tppts by the fluoro substituted sulfonated ligand 4 [Table 2 94% (n=l) and 6% (n=0)] in the rhodium-catalysed hydroformylation of 1-hexene in a two phase system increased the selectivity to linear aldehyde n-heptanal from 86% to 93% at the low P/Rh molar ratio of 7.5/1.75,76 The Rh/4 catalyst was quantitatively recovered after the reaction by simple decantation.75,76 The moderate increase of the n/i ratio is of interest when one considers that ligand 4 is mainly present as the disulfonated species (94%) compared to the trisulfonated compound tppts and that tris(4-fluorophenyl)phosphine is less basic (pKa=1.97) than triphenylphosphine (pKa=2.73).376 In rhodium-catalysed hydroformylation reactions in organic solvents it is known that electron withdrawing substituents, which increase the -acidity of the ligand, give rise to an increase in the n/i ratio.377 379... 

The commercial success of rhodium-trisulfonated triphenylphosphine (TPPTS) catalysts1 has prompted considerable interest in TPPTS and other water-soluble ligands.2 The potential for new applications for the synthesis of both bulk and fine chemicals in water has led to methods for the preparation of a wide variety of sulfonated phosphines including chiral phosphines3 and... 

An important development in the past 15 years in hydroformylation technology was the introduction of biphasic homogeneous catalysis. Kuntz (62) expressed the basic idea of a new generation of water-soluble oxo catalysts with triphenylphosphane trisulfonate (tppts as the sodium salt) as a ligand for a rhodium-complex-catalyzed hydroformylation process. Ruhrchemie AG adapted the idea on the basis of research done at Rhone-Poulenc and developed it into an industrially viable process, which was... 

The aqueous-organic two-phase system was successfully applied to perform hydrocarboxylation.300 Palladium complexes of trisulfonated triphenylphosphine ligands were shown to exhibit high activity.301-303 The application of cosolvents and modified cyclodextrins allow to eliminate solubility problems associated with the transformation of higher alkenes.304... 

Ruthenium complexes with mixed bipyridyl ligands, immobilized inside a Nation film, may also be used as pH-sensitive sensor layers [90]. A completely different approach for a ratiometric imaging of pH sensor foils was developed for diagenetic studies of marine sediments, using the dual fluorescence excitation ratio of the pH-sensitive fluorophore 8-hydroxypyrene-l,3,6-trisulfonic acid (HPTS) [91]. Commonly used dual fluorophors with different absorption and emission maxima in the protonated and basic form for ratiometric measurements are the naphthofluorescein and seminaphthofluorescein derivates (SNARF and SNAFL) [92], It should be noted that ammonia or carbon dioxide can also be detected by some of these pH-sensitive materials [55,93]. 

Initially, only dipolar aprotic solvents such as W,A -dimethylformamide (DMF), N-methylpyrrolidinone (NMP), dimethyl sulfoxide (DMSO), and acetonitrile (MeCN) were common (Table 3-2). However, the presence of water has been found to accelerate certain Heck reactions [17], and consequently the development has gone to water-soluble tiiarylphosphane ligands (e.g triphenylphosphane w-trisulfonate sodium salt (TPPTS) [18a], with which many alkene arylations succeed superbly in aqueous solvent mixtures [19]. 

Following the recommendations of Manassen [18] the history of biphasic hydroformylation began with work on various water-soluble ligands (Table 1). After this preparatory work on various aspects [30], Kuntz [22, 199] expressed the basic idea of a new generation of water-soluble oxo catalysts with triphenyl-phosphine trisulfonate (TPPT S, as the Na salt, as compared with TPPMS and TPPDS, the mono- and disulfonate) as ligands for a Rh-based oxo process, mainly for the hydroformylation of lower olefins such as propene (eq. (5)). 

The Tsuji-Trost ally lie substitution catalyzed by Pd complexes using CH-acidic nucleophiles can be performed in an ionic liquid of type 1 alone [30] as well as in a biphasic system [31]. In the latter case the use of trisulfonated triphenylphosphine (TPPTS) prevents the catalyst from leaching into the organic phase. In comparison with water as the catalyst-supporting phase, the ionic liquid system exhibits higher activity and selectivity. The enantio-selective version of the allylic substitution with dimethyl malonate can also be performed in ionic liquids with a homochiral ferrocenylphosphine as the ligand [32]. 

In the course of introducing the immobilized ligand TPPTS (triphenylphosphine trisulfonate) on an industrial production scale it was found that cations, especially ammonium and ammonium derivatives, have an extreme influence on the properties of the TPPTS salts. Even slight variations within the cations have a tremen-... 

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