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| ==Synthesis== | ==Synthesis== | ||
| TPPTS is synthesized by ] of ]. The sulfonation occurs at one meta-position of each of the three phenyl rings. The sulfonation agent is ], a solution of sulfur trioxide in sulfuric acid. |
TPPTS is synthesized by ] of ]. The sulfonation occurs at one meta-position of each of the three phenyl rings. The sulfonation agent is ], a solution of sulfur trioxide in sulfuric acid. Immediately upon dissolving in the oleum, the phosphine is protonated. It is the phosphonium salt that undergoes the sulfonation which explains its meta selectivity: | ||
| :HP(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub><sup>+</sup> + 3 SO<sub>3</sub> → <sup>+</sup> | :HP(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub><sup>+</sup> + 3 SO<sub>3</sub> → <sup>+</sup> | ||
| As a ], tppts is stronger than triphenylphosphine. | As a ], tppts is stronger than triphenylphosphine. | ||
| The synthesis of this ligand has subsequently been improved.Evidence for an interaction in water between this ligand and rhodium derivatives can be easily demonstrated. The hydrophobic complex (RhCl(cod-1,5))2 where cod1,5 is cyclooctadiene-1,5 is easily and totally dissolved in a water solution of this ligand. This property can be observed with all low-valent group VIII transition metals as well as group IB metals (Cu, Ag, Au). For example zerovalent nickel or palladium complex with triphenyl phosphine (TPP) in benzene can be extracted by a water solution of the trisulfonated ligand.One should mention that the sodium salt of (metasulfophenyl) diphenylphosphine (dpm) was prepared as early as 1958 by J. Chatt by sulfonation of the triphenylphosphine. This ligand is much less soluble in water than the trisulfonated equivalent. | |||
| ==TPPTS at the origin of two-phase homogeneous |
==TPPTS at the origin of two-phase homogeneous catalysis== | ||
| TPPTS was first synthesized in 1975 by ] who was an engineer at Rhône-Poulenc with the aim of carrying out a two-phase homogeneous catalysis in which the aqueous phase catalyst could be easily separated from the reaction products and recycled.<ref>E.Kuntz Procédé d’hydroformylation des oléfines FR 2 314 910 (20 06 1975) and FR 2 349 562 (29 04 1976) also published as US 4,248,802</ref> | TPPTS was first synthesized in 1975 by ] who was an engineer at Rhône-Poulenc with the aim of carrying out a two-phase homogeneous catalysis in which the aqueous phase catalyst could be easily separated from the reaction products and recycled.<ref>E.Kuntz Procédé d’hydroformylation des oléfines FR 2 314 910 (20 06 1975) and FR 2 349 562 (29 04 1976) also published as US 4,248,802</ref> Using TPPTS, allowed him to prepare water-soluble complexes with Rh(I), Ni(0), Pd(0). E.G. Kuntz patented several two-phase homogeneous catalytic reactions: | ||
| It's easy to separate the catalyst in heterogeneous systems, and even in homogeneous systems it is often economic to "loose" the catalyst. However, when the catalyst is expansive or toxic like Rhodium, its separation is needed especially in industrial scale and for continuous processes. One can remove the catalysts by distilling the products but heavy impurities are cumulating during industrial and recycling processes. One can also coordinate the metal to a functionnalized organic polymer but its quite very expansive. The most promising approach is to use a non miscible solvents.Using TPPTS, allowed ] to prepare water-soluble complexes with Rh(I), Ni(0), Pd(0) with a liquid separate phase. E.G. Kuntz patented several two-phase homogeneous catalytic reactions: | |||
| *hydroformylation of propylene with Rh(I) TPPTS,<ref>E.Kuntz Procédé d’hydroformylation des oléfines FR 2 314 910 (20 06 1975) and FR 2 349 562 (29 04 1976) also published as US 4,248,802</ref> later leading to the Ruhrchemie / Rhône-Poulenc process. | *hydroformylation of propylene with Rh(I) TPPTS,<ref>E.Kuntz Procédé d’hydroformylation des oléfines FR 2 314 910 (20 06 1975) and FR 2 349 562 (29 04 1976) also published as US 4,248,802</ref> later leading to the Ruhrchemie / Rhône-Poulenc process. | ||
| *hydrocyanation of olefins and dienes with Ni(0) TPPTS.<ref>E.Kuntz, Procédé d’hydrocyanation de composés organiques insaturés comportant au moins une double liaison éthylénique FR 2 338 253 (13 01 1976) also published as US 4,087,452</ref> | *hydrocyanation of olefins and dienes with Ni(0) TPPTS.<ref>E.Kuntz, Procédé d’hydrocyanation de composés organiques insaturés comportant au moins une double liaison éthylénique FR 2 338 253 (13 01 1976) also published as US 4,087,452</ref> | ||
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| The industrial use of TPPTS and homogeneous biphasic catalysis has been reviewed.<ref>Boy Cornils, Richard W. Fischer, Christian Kohlpaintner "Butanals" in Ullmann's Encyclopedia of Industrial Chemistry, 2000, Wiley-VCH, Weinheim. {{doi|10.1002/14356007.a04_447}}</ref><ref>(en) B. Cornils et É.G. Kuntz, « Hydroformylation. Development of commercial biphasic oxo synthesis », Aqueous-Phase Organometallic Catalysis, 1998, p. 271–282.</ref><ref>(en) É.G. Kuntz, « Hydrosoluble ligands for a new technology », Aqueous Organometallic Chemistry and Catalysis, 1995, p. 177-181.</ref><ref>{{cite journal|title=Introducing TPPTS and related ligands for industrial biphasic processes|first1=Boy|last1=Cornils |first2=Emile G. |last2=Kuntz|doi=10.1016/0022-328X(95)05820-F|volume=502|year=1995|page=177-186|journal=Journal of Organometallic Chemistry|issue=1–2 }}</ref> | The industrial use of TPPTS and homogeneous biphasic catalysis has been reviewed.<ref>Boy Cornils, Richard W. Fischer, Christian Kohlpaintner "Butanals" in Ullmann's Encyclopedia of Industrial Chemistry, 2000, Wiley-VCH, Weinheim. {{doi|10.1002/14356007.a04_447}}</ref><ref>(en) B. Cornils et É.G. Kuntz, « Hydroformylation. Development of commercial biphasic oxo synthesis », Aqueous-Phase Organometallic Catalysis, 1998, p. 271–282.</ref><ref>(en) É.G. Kuntz, « Hydrosoluble ligands for a new technology », Aqueous Organometallic Chemistry and Catalysis, 1995, p. 177-181.</ref><ref>{{cite journal|title=Introducing TPPTS and related ligands for industrial biphasic processes|first1=Boy|last1=Cornils |first2=Emile G. |last2=Kuntz|doi=10.1016/0022-328X(95)05820-F|volume=502|year=1995|page=177-186|journal=Journal of Organometallic Chemistry|issue=1–2 }}</ref> | ||
| ==Uses in hydroformylation |
==Uses in hydroformylation== | ||
| Complexes of TPPTS are very soluble in water, which is the basis of its industrial application. Tppts-based rhodium catalysts were introduced in 1984 for a two-phase ] of ] by the Ruhrchemie / Rhône-Poulenc process. Hydroformylation, also known as ], is the reaction of an ] with ] and ]. Traditionally, hydroformylation is catalyzed by rhodium or cobalt complexes in nonaqueous solution<ref>Boy Cornils, Richard W. Fischer, Christian Kohlpaintner "Butanals" in Ullmann's Encyclopedia of Industrial Chemistry, 2000, Wiley-VCH, Weinheim. {{doi|10.1002/14356007.a04_447}}</ref> The industrial use of Tppts and homogeneous biphasic catalysis were mostly ignored in academic research until E.G. Kuntz published a review of its previous work in 1987.<ref> É.G. Kuntz, « Homogeneous catalysis in water », Chemtech, 1987, p. 570-575</ref> Then, from 1990, use of TPPTS was rapidly become popular with thousand of citations in 2004. | Complexes of TPPTS are very soluble in water, which is the basis of its industrial application. Tppts-based rhodium catalysts were introduced in 1984 for a two-phase ] of ] by the Ruhrchemie / Rhône-Poulenc process. Hydroformylation, also known as ], is the reaction of an ] with ] and ]. Traditionally, hydroformylation is catalyzed by rhodium or cobalt complexes in nonaqueous solution<ref>Boy Cornils, Richard W. Fischer, Christian Kohlpaintner "Butanals" in Ullmann's Encyclopedia of Industrial Chemistry, 2000, Wiley-VCH, Weinheim. {{doi|10.1002/14356007.a04_447}}</ref> The industrial use of Tppts and homogeneous biphasic catalysis were mostly ignored in academic research until E.G. Kuntz published a review of its previous work in 1987.<ref> É.G. Kuntz, « Homogeneous catalysis in water », Chemtech, 1987, p. 570-575</ref> Then, from 1990, use of TPPTS was rapidly become popular with thousand of citations in 2004. | ||
| =Uses of TPPTS and homogeneous biphasic catalysis= | |||
| Homogeneous catalysis in water constitutes an original approach to the general problem of catalyst separation. These original byphasic process has exhibited the best performance in hydroformylation. This process as well as the Union Carbide one has rendered the cobalt-based process obsolete. The best ligand is the trisodium salt of tri(m-sulfonyl)phosphine.In addition to the obvious practical interest, the use of these new water-soluble ligands have opened a new area for analytical chemistry in water.It has allowed stabilization in water of transition metals and metals of group IA and IB in low oxidation state, which are sometimes unknown or unstable in water. | |||
| ==References== | ==References== | ||
| <references/> | <references/> | ||
Revision as of 12:41, 22 March 2023
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| Names | |
|---|---|
| Preferred IUPAC name Trisodium 3,3′,3′′-phosphanetriyltri(benzene-1-sulfonate) | |
Other names
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| Identifiers | |
| CAS Number | |
| 3D model (JSmol) | |
| ChemSpider | |
| ECHA InfoCard | 100.058.706 
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| EC Number |
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| PubChem CID | |
| CompTox Dashboard (EPA) | |
InChI
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SMILES
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| Properties | |
| Chemical formula | C18H12Na3O9PS3 |
| Molar mass | 568.41 g·mol |
| Appearance | White microcrystalline solid |
| Solubility in water | Soluble |
| Hazards | |
| GHS labelling: | |
| Pictograms | 
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| Signal word | Warning |
| Hazard statements | H315, H319, H335 |
| Precautionary statements | P280, P302+P352, P304+P340, P305+P351+P338, P312, P332+P313, P337+P313 |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa).
 N verify (what is ?)
Infobox references
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3,3′,3′′-Phosphanetriyltris(benzenesulfonic acid) trisodium salt (abbreviated TPPTS), is an organic compound that is also known as sodium triphenylphosphine trisulfonate. The compound has the formula P(C6H4SO3Na)3. This white solid is an unusual example of a water-soluble phosphine. Its complexes are also water-soluble. Its complex with rhodium is used in the industrial production of butyraldehyde.
Synthesis
TPPTS is synthesized by sulfonation of triphenylphosphine. The sulfonation occurs at one meta-position of each of the three phenyl rings. The sulfonation agent is oleum, a solution of sulfur trioxide in sulfuric acid. Immediately upon dissolving in the oleum, the phosphine is protonated. It is the phosphonium salt that undergoes the sulfonation which explains its meta selectivity:
- HP(C6H5)3 + 3 SO3 →
As a Lewis base, tppts is stronger than triphenylphosphine.
TPPTS at the origin of two-phase homogeneous catalysis
TPPTS was first synthesized in 1975 by E.G Kuntz who was an engineer at Rhône-Poulenc with the aim of carrying out a two-phase homogeneous catalysis in which the aqueous phase catalyst could be easily separated from the reaction products and recycled. Using TPPTS, allowed him to prepare water-soluble complexes with Rh(I), Ni(0), Pd(0). E.G. Kuntz patented several two-phase homogeneous catalytic reactions:
- hydroformylation of propylene with Rh(I) TPPTS, later leading to the Ruhrchemie / Rhône-Poulenc process.
- hydrocyanation of olefins and dienes with Ni(0) TPPTS.
- telomerization of butadiene to 2.7 octadiene -1-ol with Pd(0) TPPTS.
- The Rh(I) TPPTS catalyst was later used by D.Morel to synthesize geranylacetone from myrcene and farnesylacetone from beta-farnesene which are intermediates in the synthesis of vitamin E. This process was industrialized by Rhône-Poulenc in 1988.
The industrial use of TPPTS and homogeneous biphasic catalysis has been reviewed.
Uses in hydroformylation
Complexes of TPPTS are very soluble in water, which is the basis of its industrial application. Tppts-based rhodium catalysts were introduced in 1984 for a two-phase hydroformylation of propene by the Ruhrchemie / Rhône-Poulenc process. Hydroformylation, also known as oxo synthesis, is the reaction of an alkene with carbon monoxide and hydrogen. Traditionally, hydroformylation is catalyzed by rhodium or cobalt complexes in nonaqueous solution The industrial use of Tppts and homogeneous biphasic catalysis were mostly ignored in academic research until E.G. Kuntz published a review of its previous work in 1987. Then, from 1990, use of TPPTS was rapidly become popular with thousand of citations in 2004.
References
- GHS: Alfa Aesar 039538 (18 Feb 2021)
- Papadogianakis, G.; Maat, L.; Sheldon, R. A. (1998). "Tris[tris(Sodium m -sulfonatophenyl)-Phosphino]Palladium(0) Enneahydrate". Tris[tris(Sodium m-Sulfonatophenyl)Phosphino]Palladium(0) Enneahydrate. Inorganic Syntheses. Vol. 32. pp. 25–29. doi:10.1002/9780470132630.ch3. ISBN 9780470132630.
- Herrmann, W.A.; Kohlpaintner, C.W. (1998). Synthesis of Water-Soluble Phosphines and Their Transition Metal Complexes. Inorganic Syntheses. Vol. 32. pp. 8–25. doi:10.1002/9780470132630.ch2. ISBN 0-471-24921-1.
- E.Kuntz Procédé d’hydroformylation des oléfines FR 2 314 910 (20 06 1975) and FR 2 349 562 (29 04 1976) also published as US 4,248,802
- E.Kuntz Procédé d’hydroformylation des oléfines FR 2 314 910 (20 06 1975) and FR 2 349 562 (29 04 1976) also published as US 4,248,802
- E.Kuntz, Procédé d’hydrocyanation de composés organiques insaturés comportant au moins une double liaison éthylénique FR 2 338 253 (13 01 1976) also published as US 4,087,452
- E.Kuntz Procédé de télomérisation de diènes FR 2 366 237 (27 07 1976) also published as US 4,142,060
- D. Morel, Procédé d’addition sélective d’un composé à méthylène actif sur un diène conjugué substitué et nouveaux composés résultants FR 2 486 525 (10 07 1980) also published as US 4,460,786
- Boy Cornils, Richard W. Fischer, Christian Kohlpaintner "Butanals" in Ullmann's Encyclopedia of Industrial Chemistry, 2000, Wiley-VCH, Weinheim. doi:10.1002/14356007.a04_447
- (en) B. Cornils et É.G. Kuntz, « Hydroformylation. Development of commercial biphasic oxo synthesis », Aqueous-Phase Organometallic Catalysis, 1998, p. 271–282.
- (en) É.G. Kuntz, « Hydrosoluble ligands for a new technology », Aqueous Organometallic Chemistry and Catalysis, 1995, p. 177-181.
- Cornils, Boy; Kuntz, Emile G. (1995). "Introducing TPPTS and related ligands for industrial biphasic processes". Journal of Organometallic Chemistry. 502 (1–2): 177-186. doi:10.1016/0022-328X(95)05820-F.
- Boy Cornils, Richard W. Fischer, Christian Kohlpaintner "Butanals" in Ullmann's Encyclopedia of Industrial Chemistry, 2000, Wiley-VCH, Weinheim. doi:10.1002/14356007.a04_447
- É.G. Kuntz, « Homogeneous catalysis in water », Chemtech, 1987, p. 570-575