WO2012004352A2 - Catalyseur mésoporeux à base de complexe de diphosphine-métal de transition pour l'hydroformylation - Google Patents

Catalyseur mésoporeux à base de complexe de diphosphine-métal de transition pour l'hydroformylation Download PDF

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Publication number
WO2012004352A2
WO2012004352A2 PCT/EP2011/061531 EP2011061531W WO2012004352A2 WO 2012004352 A2 WO2012004352 A2 WO 2012004352A2 EP 2011061531 W EP2011061531 W EP 2011061531W WO 2012004352 A2 WO2012004352 A2 WO 2012004352A2
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WIPO (PCT)
Prior art keywords
transition metal
diphosphine
metal complex
mesoporous
catalyst
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PCT/EP2011/061531
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English (en)
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WO2012004352A3 (fr
Inventor
Joost Nicolaas Hendrik Reek
Marc-Olivier Coppens
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Technische Universiteit Delft
Stichting voor de Technische Wetenschappen STW
Universiteit Van Amsterdam
Original Assignee
Technische Universiteit Delft
Stichting voor de Technische Wetenschappen STW
Universiteit Van Amsterdam
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Publication of WO2012004352A2 publication Critical patent/WO2012004352A2/fr
Publication of WO2012004352A3 publication Critical patent/WO2012004352A3/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C07F15/008—Rhodium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/11—Compounds covalently bound to a solid support

Definitions

  • the invention pertains to mesoporous supported diphosphine-transition metal complexes and to use of the complex as catalyst.
  • Homogeneous transition metal catalysts generally display high activity and selectivity in contrast to their heterogeneous counterparts in hydroformylation reactions.
  • This invention relates to a transition metal catalyst for hydroformylation reactions, that upon immobilization to a support does not lose its rate compared to the homogeneous analogue, and even displays higher rates in some experiments.
  • the present invention has as one of its objectives to obtain covalently supported catalytic systems with improved activity and selectivity resembling or even improving those as obtained in homogenous reaction systems. It has now been found that this objective can be obtained by using a support with a specific pore size range, which is known as a mesoporous support.
  • mesoporous materials can lead to isolated metal species on the support surface which do not interact with each other, thus preventing in most cases their deactivation and
  • US 6,544,923 discloses a catalytic system comprising catalysts immobilized on a mesoporous support.
  • the system includes mesoporous silicate covalently bound to a ligand that in turn can covalently bind an organometallic fragment. Bonding of phosphine-transition metal ligands to the mesoporous support is not done via an aromatic system.
  • the catalytic reactions include hydrogenation,
  • CN 101642719 discloses an anchor ligand modified metal supported catalyst consisting of a mesoporous support, a metal component and an organic ligand, wherein the
  • mesoporous support is silicon dioxide, MCM-41 or SBA-15; the metal component is transition metal rhodium; and the organic ligand is an organic phosphine ligand containing an alkoxy silane group.
  • the organic ligand and the metal component are directly fixed onto the support; and simultaneously the coordination function exists between the organic ligand and the metal, and an active species is generated in situ.
  • the catalyst can be used for
  • FR 2865664 discloses a solid inorganic support, in particular a mesoporous support, modified at its surface by carrying an organic complex chelating a transition metal.
  • the organic complex has a ring structure that is unrelated to the structures as described herein.
  • the invention pertains to a diphosphine-transition metal complex comprising a
  • diphosphine-transition metal ligand that is covalently bonded to an insoluble mesoporous support, having an average pore diameter of from 4.5 nm to 50 nm, characterized in that the complex has the formula
  • R is independently aryl, C1-C4 alkyl, aralkyl, alkylaryl; Ci- C 4 alkoxy, aralkoxy, or alkylaryloxy;
  • P is a phosphorous atom
  • M is a transition metal
  • X is a bond, CH 2 , 0, S or NH 2 ;
  • Y is C or N
  • A is a linking moiety which is bonded to the mesoporous support
  • the ring formed by X, Y and the two aromatic rings is a 5- or 6-membered ring;
  • aromatic rings may be unsubstituted or substituted.
  • aryl is preferably phenyl
  • aralkyl is preferably benzyl and alkylaryl is preferably toluyl
  • alkyl is preferably methyl, ethyl or tert-butyl.
  • ethers alkoxy, aralkoxy, or alkylaryloxy
  • transition metals examples include cobalt, ruthenium, rhodium, palladium, osmium and iridium.
  • the transition metal is rhodium
  • X is 0, Y is N
  • A is a silylalkyl group when Y is N, most preferably silylpropyl, or a silylalkylidene group when Y is C
  • the ring formed by X, Y and the two aromatic groups is a 6-membered ring, and the aromatic rings are unsubstituted .
  • Catalysts comprising such an aromatic diphosphine transition metal ligand covalently bonded to a mesoporous support display a remarkably high activity in
  • hydroformylation reactions an activity that is often higher than that of its homogeneous counterpart.
  • Mesoporous supports wherein the average pore diameter is less than 4.5 nm appear to be unsuitable for stable hydroformylation catalysis, as was observed with the silicate MCM-41. It is preferred to use mesoporous supports wherein the average pore diameter is 4.5 nm to 15 nm.
  • the mesopores Preferably at least 90% of the mesopores have a diameter of 4.5 nm to 15 nm.
  • the diphosphine- transition metal complex has V micro (microporous volume) 0 - 0.2 cm 3 g -1 and V meS o (mesoporous volume) 0.5 - 2.0 cm 3 g _1 .
  • the values of the specific surface areas S BET and S mes0 pores are less important for the intrinsic properties of the catalyst, but are suitably high; values can be around 300-1000 m 2 g _1 and 200-1000 m 2 g ⁇ 1 , respectively.
  • high specific surface areas (m 2 g -1 ) (such as those of SBA-15) are an advantage, as they allow for very high chemical rates per unit mass of catalyst .
  • the ligand- mesoporous support complex has the formula:
  • n is an integer of 2 to 10 and Ph is phenyl.
  • the mesoporous support can be any support that can contain mesopores, such as silica, silicate, aluminosilicate , molecular sieves, titanium oxide, phenol/formaldehyde
  • the support is mesoporous silica.
  • the term "silica” means SiC> 2 , but the mesoporous silica may further contain small amount of other metal oxides or metal inorganic constituents. Metals that can be found in silica are aluminum, titanium, iron, calcium, magnesium, and the like, however the silica
  • a mesoporous silica preferably consist of at least 90% S1O 2 , most preferably 100% or close to 100% Si0 2 .
  • a suitable example of a mesoporous silica is SBA-15 (ex TU Delft, the Netherlands) .
  • SBA-15 a mesoporous silica with large surface area and narrow pore size
  • the rhodium-diphospine-SBA-15 material 2 was analyzed after synthesis by means of elemental analysis to determine the ligand content, based on P content, and ICP-OES analysis to determine the Rh amount.
  • the amounts of rhodium and ligand present on the silica mesoporous support were estimated to be around 1.0 ⁇ 10 ⁇ 5 mole/g and 1.5 ⁇ 10 ⁇ 4 mole/g SBA-15 respectively (i.e. ligand-to-metal ratio of 15).
  • Rhodium complex 2 supported on silica gel indeed shows activities (TOF of 8; TOF is average turn over frequency) that are 15 times lower than its homogeneous analogue (TOF of 120, entry 25) . Also the
  • regioselectivity is slightly lower (1/b of 19; 1/b is the linear/branched ratio) when applied under the same catalytic conditions.
  • the rhodium catalyst supported on mesoporous SBA- 15 showed much better performance in the hydroformylation reaction than the silica gel supported analogue (Table 1; entries 1-17, 24) .
  • the SBA-15 supported catalyst 2 showed high activities with a TOF up to 195 and a 1/b regioselectivity of around 34 (Table 1; entries 1-17), demonstrating that both activity and selectivity are much higher than those of the catalyst immobilized on amorphous silica support (Table 1; entry 24).
  • the activity is comparable with, and in some experiments higher than that of the homogeneous catalyst used under the same catalytic conditions (entries 1, 4-6, 8- 10, 15-17 and 25, respectively) .
  • catalyst 2 supported on SBA-15 showed activities (TOF of 306 to 995) that are 2 to 7 times as high as the homogeneous rhodium complex (entries 8-10 and 26, respectively) , while the regioselectivity is slightly lower (92% of linear product compared to 96% for the homogeneous phase) .
  • the hydroformylation reaction using the SBA-15 supported catalyst 2 was performed in pure substrate resulting in very high activities and very high TON' s (entries 9-17; TON is Turn
  • the reproducibility of the catalyst immobilization was studied by making a batch of supported ligand using the same batch of silica SBA-15 under identical conditions.
  • the SBA-15 metal complex 2 showed slightly decreased performance when this second batch was applied in the hydroformylation reaction (Table 1; entries 18-23) . While selectivity remains comparable to the previous batch of SBA-15 material (linear over branched ratios around 30 and 40 respectively at 50 and 20 bars of syn-gas pressure) , the activities decreased by almost a factor 2, with TOF' s going down to 100 and 192 for the process at 50 and 20 bars, respectively.
  • the decreased catalytic performance is also observed in terms of stability of the catalytic material. While the first batch of supported metal complex 2 was recycled up to 15 times leading to a cumulative TON of 67716, the second batch of supported
  • the catalysts as described herein may advantageously be used in catalytic reactions like hydrogenation, carbonylation and carbon-carbon coupling reactions.
  • the catalysts can be used for hydrogenation of any compound containing an olefin moiety.
  • silica gel was dissolved in 48% aqueous HF (1 mL x 50 mg of silica) and heated under vacuum at 80 °C until all the volatiles were evaporated. The residue was dissolved by adding fuming nitric acid (2 mL) and warming up the solution to 90 °C for 1 hour. Hydrogen peroxide (few drops) was added to the warm sample until the solution became colorless. Water was added to bring the total volume up to 10 mL for analysis. Loading: 0.17 mmole/g.
  • the high-pressure IR spectra were performed in a stainless steel (SS 316) 50 mL autoclave equipped with ZnS windows (700 cm -1 , i.d. 10 mm, optical path length 0.4 mm), a mechanical stirrer, a temperature controller, and a pressure device.
  • ZnS windows 700 cm -1 , i.d. 10 mm, optical path length 0.4 mm
  • a mechanical stirrer a temperature controller
  • a pressure device a pressure device.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention porte sur un complexe de diphosphine-métal de transition comprenant un ligand diphosphine-métal de transition qui est lié de façon covalente à un support mésoporeux insoluble ayant un diamètre moyen des pores de 4,5 nm à 50 nm, caractérisé en ce que le ligand tel que fixé au support répond à la formule : dans laquelle R représente un groupe aryle, alkyle en C1-C4, aralkyle, alkylaryle, alcoxy en C1-C4, aralcoxy ou alkylaryloxy ; P représente un atome de phosphore ; M représente un métal de transition ; X représente une liaison CH2, O, S ou NH2 ; Y représente C ou N ; A représente une fraction de liaison qui est liée au support mésoporeux ; le noyau formé par X, Y et les deux noyaux aromatiques est un noyau à 5 ou 6 chaînons ; les noyaux aromatiques peuvent être non substitués ou substitués. L'invention porte en outre sur l'utilisation du complexe de diphosphine-métal de transition comme catalyseur dans une réaction choisie parmi l'hydroformylation, l'hydrogénation, la carbonisation ou le couplage carbone-carbone.
PCT/EP2011/061531 2010-07-08 2011-07-07 Catalyseur mésoporeux à base de complexe de diphosphine-métal de transition pour l'hydroformylation Ceased WO2012004352A2 (fr)

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EP10168873.7 2010-07-08
EP10168873 2010-07-08

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WO2012004352A2 true WO2012004352A2 (fr) 2012-01-12
WO2012004352A3 WO2012004352A3 (fr) 2012-03-08

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105772095A (zh) * 2016-04-22 2016-07-20 太原理工大学 一种铑金属配合物介孔催化剂及其制备和应用
US11607678B1 (en) 2021-08-18 2023-03-21 Saudi Arabian Oil Company Surface supported catalysts with pore size control

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6544923B1 (en) 1999-08-25 2003-04-08 Massachusetts Institute Of Technology Surface-confined catalytic compositions
FR2865664A1 (fr) 2004-02-04 2005-08-05 Saint Gobain Rech Solides inorganiques, notamment poreux, en particulier mesoporeux, modifies par des molecules organiques chelatant des metaux de transition, leur preparation et leur utilisation comme catalyseurs
CN101642719A (zh) 2008-08-07 2010-02-10 中国科学院大连化学物理研究所 一种锚合配体修饰的负载金属催化剂及制备方法和应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6544923B1 (en) 1999-08-25 2003-04-08 Massachusetts Institute Of Technology Surface-confined catalytic compositions
FR2865664A1 (fr) 2004-02-04 2005-08-05 Saint Gobain Rech Solides inorganiques, notamment poreux, en particulier mesoporeux, modifies par des molecules organiques chelatant des metaux de transition, leur preparation et leur utilisation comme catalyseurs
CN101642719A (zh) 2008-08-07 2010-02-10 中国科学院大连化学物理研究所 一种锚合配体修饰的负载金属催化剂及制备方法和应用

Non-Patent Citations (6)

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"Catalyst Separation, Recovery and Recycling: Chemistry and Process Design", 2006, SPRINGER
A. J. SANDEE, J. N. H. REEK, P. C. J. KAMER, P. W. N. M. VAN LEEUWEN, J. AM. CHEM. SOC., vol. 123, 2001, pages 8468
A. J. SANDEE, L. A. VAN DER VEEN, J. N. H. REEK, P. C. J. KAMER, M. LUTZ, A. L. SPEK, P. W. N. M. VAN LEEUWEN, ANGEW. CHEM. INT. ED. ENGL., vol. 38, 1999, pages 3231
D. ZHAO, J. FENG, Q. HUO, N. MELOSH, G. H. FREDRICKSON, B. F. CHMELKA, G. D. STUCKY, SCIENCE, vol. 279, 1998, pages 548
D. ZHAO, Q. HUO, J. FENG, B. F. CHMELKA, G. D. STUCKY, J. AM. CHEM. SOC., vol. 120, 1998, pages 6024
FABRIZIO MARRAS, JIA WANG, MARC-OLIVIER COPPENS, JOOST N. H. REEK: "Ordered Mesoporous Materials as Solid Supports for rhodium-diphosphine catalysts with remarkable hydroformylation activity", CHEMICAL COMMUNICATIONS, vol. 46, 2010, pages 6587 - 6589

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105772095A (zh) * 2016-04-22 2016-07-20 太原理工大学 一种铑金属配合物介孔催化剂及其制备和应用
US11607678B1 (en) 2021-08-18 2023-03-21 Saudi Arabian Oil Company Surface supported catalysts with pore size control

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