WO2002024713A1 - Complexes de ruthenium dicationiques et leur utilisation pour des reactions de metathese d'olefines - Google Patents

Complexes de ruthenium dicationiques et leur utilisation pour des reactions de metathese d'olefines Download PDF

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Publication number
WO2002024713A1
WO2002024713A1 PCT/EP2001/010778 EP0110778W WO0224713A1 WO 2002024713 A1 WO2002024713 A1 WO 2002024713A1 EP 0110778 W EP0110778 W EP 0110778W WO 0224713 A1 WO0224713 A1 WO 0224713A1
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WO
WIPO (PCT)
Prior art keywords
ruthenium complexes
complexes
independently
general formula
another
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PCT/EP2001/010778
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German (de)
English (en)
Inventor
Wolfram STÜER
Michael Röper
Stefan Jung
Justin Wolf
Helmut Werner
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Basf Aktiengesellschaft
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Priority to AU2002221605A priority Critical patent/AU2002221605A1/en
Publication of WO2002024713A1 publication Critical patent/WO2002024713A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • 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
    • C07F15/0046—Ruthenium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium

Definitions

  • the invention relates to new dicationic ruthenium complexes, their preparation and use.
  • WO-A-99/58538 discloses cationic carbene complexes of ruthenium which carry a positive charge per ruthenium center.
  • the object was therefore to provide cationic carbene complexes which remedy the disadvantages mentioned above.
  • R 1 , R 2 , R 3 , R 4 independently of one another are hydrogen, Ci to C 0 alkyl, C 1 to C n-haloalkyl or an optionally one to five times by C 1 to C 6 alkyl, halogen and / or cyano substituted aryl or C - to C 2 n-aralkyl,
  • X, Y independently weak or non-coordinating anionic radical L 1 , L 2 , L 3 , L 4 , L 5 independently of one another neutral 2-electron donor ligands or two or more chelate ligands connected to one another by a bridge
  • n independently of one another 0 or 1.
  • the dicationic ruthenium complexes I obtained in this way can be used in situ as a catalyst system without activation or activated with an acid HY or an alkylating agent RY or stored in isolation under an inert gas atmosphere.
  • the dicationic ruthenium complexes I may be used in isolated form.
  • Suitable organic solvents are hydrocarbons, for example C 5 -C 8 -alkanes such as n-pentane, isopentane, pentane mixtures, n-hexane, iso-hexane, hexane mixtures, n-heptane, iso-heptane , Heptane mixtures, n-octane, iso-octane, octane mixtures, n-nonane, iso-nonane, nonane mixtures, n-decane, iso-decane, decane mixtures, n-dodecane, iso-dodecane , Dodecane mixtures or mixtures thereof, ethers, for example diaryl ethers such as diphenyl ether or C 3 -C 6 -dialkyl ethers such as methyl ether, methyl ethyl ether, diethyl ether, methyl
  • butyl ether or mixtures thereof alcohols, for example C 3 - to C 2 o ⁇ alkanols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, butanol isomers or mixtures thereof, esters, for example C to C 2 n-carboxylic acid - esters such as methyl formate, methyl acetate, ethyl acetate or mixtures thereof, halogenated hydrocarbons, for example C 1 -C 4 -chloroalkanes such as methylene chloride, chloroform, carbon tetrachloride or mixtures thereof, carboxylic acids, for example C 1 -C 8 -carboxylic acids such as formic acid , Acetic acid, propionic acid or mixtures thereof, nitriles, for example C - to C o ⁇ alkyl nitriles such as acetonitrile or aryl nitriles
  • inert gases are suitable as inert gases, for example nitrogen and noble gases such as argon, preferably argon.
  • Suitable as the cation M are metal ions, such as monovalent metal ions, for example lithium, sodium, potassium, cesium, copper, silver, thallium, phosphonium, ammonium and carbenium, preferably silver and thallium, particularly preferably silver.
  • radicals R 1 , R 2 , R 3 , R 4 , X and Y and the ligands L 1 , L 2 , L 3 , L 4 and L 5 and the indices m and n have the following meanings:
  • R 1 , R 2 , R 3 , R 4 independently of one another are hydrogen, --CC ⁇ to C 0 alkyl, preferably -C ⁇ to Cs-alkyl such as methyl,
  • C ⁇ ⁇ to Co-haloalkyl preferably C ⁇ ⁇ to C 4 haloalkyl, particularly preferably C ⁇ ⁇ to C 4 -fluoro, chloro and / or bromoalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, Dibromomethyl, tribromomethyl,
  • Aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl and 9-anthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl, by C 1 -C 4 -alkyl, halogen and / or cyano mono- to pentasubstituted aryl, preferably by C 1 -C 4 -alkyl, fluorine, chlorine, bromine and / or cyano monosubstituted to trisubstituted phenyl, particularly preferably by methyl, ethyl, fluorine, chlorine and / or Cyano mono- to trisubstituted phenyl such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2, 5-dimethylphenyl, 2,6-dimethylphenyl, 3, 4-dimethyl
  • X, Y independently of one another, weakly or non-coordinating, anionic radicals, for example phosphates, sulfates, borates, perchlorates and sulfonates, preferably PF 5 , BF 4 , B [C 6 H 5 ] 4 , B [C 6 F 5 ] 4 ,
  • L 1 , L 2 , L 3 , L, L 5 independently of one another - neutral 2-electron donor ligands, for example amines such as primary amines, secondary amines, tertiary amines, for example trimethylamine or tetramethylene diamine, nitriles such as acetoni- tril or benzonitrile, preferably CH 3 CN, aromatics, for example benzene, toluene or xylenes, aromatic carboxylic acids such as picric acid, ketones, for example acetone, aldehydes, ammonia, water, carbon monoxide, phosphines such as phosphines with aliphatic, aliphatic-aromatic or aromatic substituents, for example P (isopropyl) 3 , P (cyclohexyl) 3 , P (CH 3 ) 2 (C 6 H 5 ), P (CH 3 ) (C 6 H 5 ) 2 , P (C
  • R 1 is hydrogen
  • the ligands L 1 and L 2 have in particular the following meanings: L 1 , L 2 independently of one another
  • These catalysts are suitable for chemical reactions such as hydrogenations and addition reactions such as additions of CHC1 3 to olefins, in particular for metathesis reactions of olefins, such as self-metathesis of an olefin or cross-metathesis of two or more olefins, ring-opening metathesis polymerization (ROMP) of cyclic olefins, selective ring opening of cyclic olefins with acyclic olefins, acyclic diene metathesis polymerisation (ADMET), ring closure metathesis (RCM) and other new types of metathesis.
  • olefins such as self-metathesis of an olefin or cross-metathesis of two or more olefins, ring-opening metathesis polymerization (ROMP) of cyclic olefins, selective ring opening of cyclic olefins with acyclic olefins, acycl

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne des complexes de ruthénium dicationiques de formule générale (I) dans laquelle R?1, R2, R3, R4¿ sont indépendamment hydrogène, alkyle en C¿1? à C20, halogénalkyle en C1 à C20 ou un aryle éventuellement substitué de une à cinq fois par alkyle en C1 à C8, halogène et/ou cyano, ou aralkyle en C7 à C20; X et Y sont indépendamment un radical anionique faiblement ou non coordonnateur; L?1, L2, L3, L4, L5¿ sont indépendamment des ligands de donneurs de deux électrons neutres ou au moins deux ligands de chélation liés ensemble par un pont; et m et n valent indépendamment 0 ou 1.
PCT/EP2001/010778 2000-09-19 2001-09-18 Complexes de ruthenium dicationiques et leur utilisation pour des reactions de metathese d'olefines WO2002024713A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002221605A AU2002221605A1 (en) 2000-09-19 2001-09-18 Dicationic ruthenium complexes and use of the same for olefin metathesis reactions

Applications Claiming Priority (2)

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DE10046540 2000-09-19
DE10046540.4 2000-09-19

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WO2002024713A1 true WO2002024713A1 (fr) 2002-03-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109225334A (zh) * 2018-07-20 2019-01-18 吉林化工学院 一种具有邻位空间位阻结构的钌烯烃复分解催化剂及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999000396A1 (fr) * 1997-06-25 1999-01-07 Ciba Specialty Chemicals Holding Inc. Catalyseurs de type carbene de ruthenium et d'osmium
WO1999026949A1 (fr) * 1997-11-21 1999-06-03 California Institute Of Technology Derives de base de schiff de catalyseurs de ruthenium et d'osmium servant a effectuer la metathese d'olefines
DE19800934A1 (de) * 1997-08-22 1999-07-15 Basf Ag Verfahren zur Herstellung von Rutheniumkomplexen
WO1999058538A1 (fr) * 1998-05-08 1999-11-18 Basf Aktiengesellschaft Complexes cationiques de ruthenium, leur preparation et leur utilisation
EP1024144A2 (fr) * 1999-01-29 2000-08-02 Zeon Chemicals L.P. Catalyseurs de ruthénium pour des réactions de méthathèse des oléfines

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999000396A1 (fr) * 1997-06-25 1999-01-07 Ciba Specialty Chemicals Holding Inc. Catalyseurs de type carbene de ruthenium et d'osmium
DE19800934A1 (de) * 1997-08-22 1999-07-15 Basf Ag Verfahren zur Herstellung von Rutheniumkomplexen
WO1999026949A1 (fr) * 1997-11-21 1999-06-03 California Institute Of Technology Derives de base de schiff de catalyseurs de ruthenium et d'osmium servant a effectuer la metathese d'olefines
WO1999058538A1 (fr) * 1998-05-08 1999-11-18 Basf Aktiengesellschaft Complexes cationiques de ruthenium, leur preparation et leur utilisation
EP1024144A2 (fr) * 1999-01-29 2000-08-02 Zeon Chemicals L.P. Catalyseurs de ruthénium pour des réactions de méthathèse des oléfines

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Title
GERARD H ET AL: "FATE OF CH2=CHE (E = H, OME) IN THE PRESENCE OF UNSATURATED RU(X)(H)L2Q+ (X = CL, Q = 0;X = CO, Q = 1): HIGHLY SENSITIVE TO X AND E", ORGANOMETALLICS, ACS, COLUMBUS, OH, US, vol. 19, no. 12, 12 June 2000 (2000-06-12), pages 2291 - 2298, XP001056005, ISSN: 0276-7333 *
GRUENWALD ET AL: "Five-Coordinate 16-Electron Carbene- and Vinylideneruthenium(II) Complexes Prepared from [RuCl2(C8H12)]n or from the New Dihydridoruthenium(IV) Compound [RuH2Cl2(PiPr3)2]", ORGANOMETALLICS, WASHINGTON, DC, US, vol. 15, no. 8, 16 April 1996 (1996-04-16), pages 1960 - 1962, XP002107199, ISSN: 0276-7333 *
HANSEN S M ET AL: "THE FIRST GRUBBS-TYPE METATHESIS CATALYST WITH CIS STEREOCHEMISTRY:SYNTHESIS OF (ETA2-DTBPM)CL2RU=CH-CH=CME2 FROM A NOVEL, COORDINATIVELY UNSATURATED DINUCLEAR RUTHENIUM DIHYDRIDE", CHEMISTRY - A EUROPEAN JOURNAL, VCH PUBLISHERS, US, vol. 5, no. 2, 1 February 1999 (1999-02-01), pages 557 - 566, XP001027489, ISSN: 0947-6539 *
JUNG S ET AL: "CATIONIC VINYL AND DICATIONIC CARBENE RUTHENIUM(II) COMPLEXES FROM A VINYLIDENE(HYDRIDO) PRECURSOR", ORGANOMETALLICS, ACS, COLUMBUS, OH, US, vol. 20, no. 11, 28 May 2001 (2001-05-28), pages 2121 - 2123, XP001056006, ISSN: 0276-7333 *
KATAYAMA H ET AL: "CONVENIENT ROUTES TO VINYLIDENERUTHENIUM DICHLORIDES WITH BASIC AND BULKY TERTIARY PHOSPHINE LIGANDS (PPRI3 AND PCY3)", ORGANOMETALLICS, WASHINGTON, DC, US, vol. 17, no. 23, 9 November 1998 (1998-11-09), pages 5190 - 5196, XP001027488, ISSN: 0276-7333 *
OLIVAN M ET AL: "HYDRIDE IS NOT A SPECTATOR LIGAND IN THE FORMATION OF HYDRIDO VINYLIDENE FROM TERMINAL ALKYNE AND RUTHENIUM AND OSMIUM HYDRIDES: MECHANISTIC DIFFERENCES", ORGANOMETALLICS, WASHINGTON, DC, US, vol. 17, no. 14, 6 July 1998 (1998-07-06), pages 3091 - 3100, XP001027487, ISSN: 0276-7333 *
WILHELM T E ET AL: "REACTIVITY OF RU(H)(H2)CL(PCY3)2 WITH PROPARGYL AND VINYL CHLORIDES: NEW METHODOLOGY TO GIVE METATHESIS-ACTIVE RUTHENIUM CARBENES", ORGANOMETALLICS, WASHINGTON, DC, US, vol. 16, no. 18, 2 September 1997 (1997-09-02), pages 3867 - 3869, XP001027486, ISSN: 0276-7333 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109225334A (zh) * 2018-07-20 2019-01-18 吉林化工学院 一种具有邻位空间位阻结构的钌烯烃复分解催化剂及其制备方法和应用
CN109225334B (zh) * 2018-07-20 2021-05-18 吉林化工学院 一种具有邻位空间位阻结构的钌烯烃复分解催化剂及其制备方法和应用

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