Water-soluble tris phosphine

More recently, Atwood et al. developed a platinum complex of a water-soluble, bidentate phosphine ligand, cA-(TPPTS)2PtCl2 [TPPTS = tris(sodium m -benzenesuI onatc)phosphi nc, as an effective hydration... 

Ellis, J.W., Harrison, K.N., Hoye, P.A.T., Orpen, A.G., Pringle, P.G., and Smith, M.B., Water-soluble tris(hydroxymethyl)phosphine complexes with nickel, palladium, and platinum. Crystal structure of Pd P(CH2OH)3 4].cntdot.CH3, Inorg. Chem., 31, 3026, 1992. 

With the knowledge that 14 can activate aldehydes in 1, the role of 1 in the reaction was explored further. Specifically, the relative rates of C—H bond activation and guest ejection, and the possibility of ion association with 1, were investigated. The hydrophobic nature of 14 could allow for ion association on the exterior of 1, which would be both cn t h al pi cal I y favorable due to the cation-it interaction, and entropically favorable due to the partial desolvation of 14. To explore these questions, 14 was irreversibly trapped in solution by a large phosphine, which coordinates to the iridium complex and thereby inhibits encapsulation. Two different trapping phosphines were used. The first, triphenylphosphine tris-sulfonate sodium salt (TPPTS), is a trianionic water-soluble phosphine and should not be able to approach the highly anionic 1, thereby only trapping the iridium complex that has diffused away from 1. The second phosphine, l,3,5-triaza-7-phosphaadamantane (PTA), is a water-soluble neutral phosphine that should be able to intercept an ion-associated iridium complex. 

The water-soluble tris(2-carboxyethyl)phosphine (TCEP) was synthesized and used to cleave rapidly organic disulfides to sulfhydryls in water (Burns et al., 1991). The... 

Other water-soluble tertiary phosphines can be used as ligands for the synthesis of hydrogenation catalysts. An example of such a phosphine is l,3>5-triaza-7-phosphaadamantane, which has been prepared by reacting tris(hydroxymethyl) phosphine, formaldehyde, and hexamethylenetetramine (Eq. 35) (111,112). The ruthenium(ll) complex of 1,3,5-triaza-7 phos-... 

The Ruhrchemie/Rhone-Poulenc Oxo process (Figure 4.1, Scheme 4.1) was developed for the synthesis of butyraldehyde from propylene and synthesis gas, where the water-soluble tris(m-sulfonated-phenyl)phosphine (TPPTS)-modified rhodium catalyst operates in the aqueous phase [14]. 

Bulky tri(o-tolyl)phosphine was used first by Heck [11]. A palladacycle obtained from it is known as the Herrmann complex (XVIII-1) and is used extensively in HR [12]. Also, palladacycles XVIII-7 [13] and XVIII-2 [14] are high performance catalysts. Turnover numbers as high as 630-8900 were achieved by tetraphosphine Tedicyp (X-1) [15]. Recently, the remarkable effect of electron-rich and bulky phosphines, typically P(t-Bu)3 and other phosphines shown in Tables 1.4, 1.5 and 1.6, have been vmveiled. Smooth reactions of aryl chlorides using these ligands are treated later. Electron-rich ligands accelerate oxidative addition of aryl chlorides, and reductive elimination is accelerated by bulky ligands. HR can be carried out in an aqueous solution by use of a water-soluble sulfonated phosphine (TPPMS, II-2) [16]. 

This reaction has been extended to form 3-methylindole in higher yields and under milder conditions without using a phosphine ligand.In addition, the cyclization of o-halo-A-allylanilines has been performed in a homogeneous water/CHsCN medium in the presence of a water soluble tris(3-sulfonatophenyl)phosphine sodium salt (TPPTS) ligand, and in supercritical CO2 in the presence of Pd(OAc)2 and a fluorinated phosphine ligand, e.g., phenyl bis(2-perfluorohexyl)-ethylphosphine. ... 

Another prominent catalytic system uses the water-soluble tris(guadinophenyl)-phosphine 22 to carry out reactions between two anionic species (Scheme 9.9)... 

Scheme 9.9 Water-soluble tris(guadinophenyl)phosphine 22 and triphenylphosphinetrisulfonate trisodium salt (26) used to cross-couple anionic p-iodobenzoate 23 with propiolate 24 to give phenylacetylene 25 in aqueous media [67dj.

Finally a variety of 1-alkenes were hydroformylated with a highly water-soluble tris-sulphonated ligand, P(m-PhS03Na). Some more effective catalysts involving the use of other sulphonated phosphine ligands have also been developed. ... 

Much research has been devoted to water-soluble sulfonated phosphines and, in particular, the well-known TPPTS (triphenylphosphine tris-sulfonated sodium salt) ligand used in propene hydroformylation on an industrial scale by Ruhrchemie/ Rhone-Poulenc since 1982 (Figure 6.8) [9, 10]. 

A new homogeneous process for hydroformylation of olefins using a water-soluble catalyst has been developed (40). The catalyst is based on a rhodium complex and utilizes a water-soluble phosphine such as tri(M-sulfophenyl)phosphine. The use of an aqueous phase simplifies the separation of the catalyst and products (see Oxo process). 

New Chemistry, Including Pulp Bleaching Processes, of the Golden-Aged, Water-Soluble Compound, Tris(hydroxymethyl)phosphine... 

Nickel(0) complexes with water-soluble phosphines have attracted interest in the context of homogeneous catalysis. A comprehensive study of the coordination chemistry of tris(sodium-m-sulfonatophenyl)phosphine (1039) has appeared.2504 The complexes [Ni(CO)2(1039)2] 6HzO have been made by reaction of (1039) with Ni(CO)4 under phase-transfer conditions, and the homo-leptic [Ni(1039)3]-9H2O has been made from Ni° precursors and (1039) under phase-transfer conditions, or from NiCl2, (1039), and BH4 in water. A related complex [Ni(CO)2(1040)2] with the bidentate ligand (1040) has also been studied.2505... 

The RCH/RP process converts propylene to n- and Lo-butyraldehydes (or butenes to valeraldehydes) in the presence [HRh(CO)(TPPTS)] (with TPPTS = tris[sodium-m-sulfonatophcnvl phosphine as water soluble ligand) according to Equation 5.1. 

Condensation of tris(hydroxymethyl)phosphine with easily available water soluble secondaiy amines yielded the hydrophihc... 

To circumvent the formation of ditelomers and to attempt recycling of the catalysts, the telomerization of polyols was studied in the presence of water using water soluble catalysts such as Pd/TPPTS (TPPTS = tris(m-sulfonato-phenyl) phosphine trisodium salt) [9, 12, 16, 17]. Behr et al. studied the telomerization of ethylene glycol under biphasic conditions. Under such reaction conditions, 80% of mono-telomer are formed and only traces of ditelomer and butadiene dimers are detected (Fig. 4). This is attributed to the solubility of the monomer in the catalyst phase. However, the catalyst is unstable and decomposes rapidly, leading to almost inactive catalyst after three runs. This is due to TPPTS oxidation during the work-up of the reaction and can be avoided by addition of 2.5 equiv. ligand in the solution prior to each run. 

The latest development in industrial alkene hydroformylation is the introduction by Rurhchemie of water-soluble sulfonated triphenylphosphine ligands.94 Hydroformylation is carried out in an aqueous biphasic system in the presence of Rh(I) and the trisodium salt of tris(m-sulfophenyl)phosphine (TPPTN). High butyraldehyde selectivity (95%) and simple product separation make this process more economical than previous technologies. 

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