Water-soluble catalysts, based triphenylphosphine

Subsequently, water-soluble catalysts have been developed for use in aqueous biphasic systems. One such catalyst precursor is RuHCl(TPPTS)2(L)2 (where TPPTS = triphenylphosphine trisulfonate and L = aniline or a similar base). 

Synthesis of the first water-soluble catalyst complexes was reported in 1973 [3] and was based on the use of sulfonated triphenylphosphine to replace TPP. The sulfonated derivative was found to stabilize the lower oxidation states of a number of transition metals such as Rh, Ru, Ir, Pt, Ni, and Cu in aqueous systems and these water-soluble catalysts facilitated hydrogenation of soluble substrates like pyruvic acid. 

Cuprous chloride tends to form water-soluble complexes with lower olefins and acts as an IPTC catalyst, e.g., in the two-phase hydrolysis of alkyl chlorides to alcohols with sodium carboxylate solution [10,151] and in the Prins reactions between 1-alkenes and aqueous formaldehyde in the presence of HCl to form 1,3-glycols [10]. Similarly, water-soluble rhodium-based catalysts (4-diphenylphosphinobenzoic acid and tri-Cs-io-alkylmethylam-monium chlorides) were used as IPTC catalysts for the hydroformylation of hexene, dodecene, and hexadecene to produce aldehydes for the fine chemicals market [152]. Palladium diphenyl(potassium sulfonatobenzyl)phosphine and its oxide complexes catalyzed the IPTC dehalogenation reactions of allyl and benzyl halides [153]. Allylic substrates such as cinnamyl ethyl carbonate and nucleophiles such as ethyl acetoactate and acetyl acetone catalyzed by a water-soluble bis(dibenzylideneacetone)palladium or palladium complex of sulfonated triphenylphosphine gave regio- and stereo-specific alkylation products in quantitative yields [154]. Ito et al. used a self-assembled nanocage as an IPTC catalyst for the Wacker oxidation of styrene catalyzed by (en)Pd(N03) [155]. 

In addition to pyridinium based catalysts and cyclodextrin derivatives, some special compounds have also been reported to be useful inverse PT catalysts for specific reactions. Te-tramethyl ammonium salts that are ineffective as PT catalysts due to their high solubility in the aqueous phase have been found to be effective inverse PT catalysts in some systems. Some metal compounds like platinum, palladium, and rhodium can strongly complex with water-soluble ligands such as the trisodium salt of triphenylphosphine trisulfonic acid, and act as effective inverse PT catalysts. These complexes are soluble in the aqueous phase only and, thus are easily recov-... 

Rhone-Poulenc and Ruhrchemie (now Hoechst) developed a process in the 1980s based on a water soluble rhodium catalyst modified with triphenylphosphine sulphonate ligand that can produce normal to iso ratios as high as 20. Previous phosphine modified rhodium catalysts were oil soluble. 

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