Triphenylphosphine m-trisulfonate

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). 

Sulfonated triphenylphosphine [TPPTS (triphenylphosphine, m-trisulfonated) tri(m-sulfophenyl)phosphine] (II-l) and monosulfonated triphenylphosphine [TP-PMS (triphenylphosphine, monosulfonated) 3-(diphenylphosphino)benzenesul-fonic acid] (II-2) are commercially available ligands and their sodium salts are water-soluble [15]. The Na salt of the ligand TPPTS is very soluble and may be too soluble in water, hence moderately soluble TPPMS is preferred. Another water-soluble phosphine is 2-(diphenylphosphinoethyl)trimethyl ammonium halide (II-11) [16]. A number of other water-soluble phosphines are now known (Table 1.2). Pd complexes, coordinated by these phosphines, are soluble in water, and Pd-catalyzed reactions can be carried out in water, which is said to have an accelerating effect in some catalytic reactions. 

Initially, only dipolar aprotic solvents such as dimethylformamide (DMF), N-methylpyrrohdinone (NMP), dimethyl sulfoxide (DMSO), acetonitrile (MeCN), and anisole were common (Table 8.2). However, the presence of water has been found to accelerate certain Heck reactions [82, 83], and consequently, the development has gone to water-soluble triarylphosphine ligands (e.g., triphenylphosphine-m-trisulfonic acid sodium salt (TPPTS) [56a]) with which many alkene arylations... 

Commercially, the aqueous-phase concept was firstly applied in Ruhrchemie/Rhone-Poulenc s (RCH/RP) process (for the fundamentals, see Section 2.4.1.1). In several units the RCH/RP process has been converting propene to n-butyraldehyde and isobutyraldehyde (or butenes to valeraldehydes) since 1984 in the presence of HRh(CO)(TPPTS)3 (with TPPTS = m-trisulfonated triphenylphosphine or tris-(sodium-fn-sulfonatophenyl)phosphine as water-soluble ligand) according to Eq. (1). The output of the units mentioned is approximately890 000 tpy, which corresponds to roughly 13% of the world s total production. 

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. 

Researchers at INTEVEP SA (Ven) have recently shown that the regioselective hydrogenation of benzo[fo]thiophene (BT) to dihydrobenzo[fo]thiophene (DHBT) (Eq. 2) can be performed in a 1 1 water/decalin mixture using an in situ catalyst system formed by addition of an excess of either m-monosulfonated triphenylphos-phine (TPPMS) or trisulfonated triphenylphosphine (TPPTS) to various Ru(II) precursors [2 a], It is believed that the catalytically active species is a mononuclear Ru(II) complex with chloride and hydride ligands. 

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