WO2002024713A1 - Dicationic ruthenium complexes and use of the same for olefin metathesis reactions - Google Patents

Dicationic ruthenium complexes and use of the same for olefin metathesis reactions Download PDF

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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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ruthenium complexes
complexes
independently
general formula
another
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PCT/EP2001/010778
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German (de)
French (fr)
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Wolfram STÜER
Michael Röper
Stefan Jung
Justin Wolf
Helmut Werner
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Basf Aktiengesellschaft
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    • 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

The invention relates to dicationic ruthenium complexes of general formula (I) wherein R?1, R2, R3, R4¿ independently represent hydrogen, C¿1? to C20 alkyl, C1 to C20 halogen alkyl, or an aryl or C7 to C20 aralkyl optionally substituted one to five times by C1 to C8 alkyl, halogen and/or cyano; X, Y independently represent weakly or non-coordinating, anionic radicals; L?1, L2, L3, L4, L5¿ independently represent neutral 2-electron donor ligands or at least two chelate ligands linked together by a bridge; and m, n independently represent 0 or 1.

Description

FUTTERMITTEL ODER FUTTERMITTELZUSATZ ALS LEISTUNGSFORDERER ODER APPETITFOR- FEED OR ADDITIVES AS A PERFORMANCE OR APPLICATION
DERER FÜR NUTZTIERETHOSE FOR FARM ANIMALS
Beschreibungdescription
Die Erfindung betrifft neue dikationische Rutheniumkomplexe, deren Herstellung und Verwendung.The invention relates to new dicationic ruthenium complexes, their preparation and use.
Aus der WO-A-99/58538 sind kationische Carben-Komplexe des Ru- theniums, die eine positive Ladung pro Ruthenium-Zentrum tragen, bekannt.WO-A-99/58538 discloses cationic carbene complexes of ruthenium which carry a positive charge per ruthenium center.
Aus Chem. Eur. J. 1999, Heft 5, Seiten 557 bis 566 sind weitere kationische Carben-Komplexe monomerer oder dimerer Grundstruktur mit cis-Phosphanen bekannt.Further cationic carbene complexes of monomeric or dimeric basic structure with cis-phosphines are known from Chem. Eur. J. 1999, volume 5, pages 557 to 566.
Diese Verbindungen sind jedoch bei Raumtemperatur in ihrer Stabilität verbesserungsbedürftig.However, the stability of these compounds is in need of improvement at room temperature.
Es bestand daher die Aufgabe kationische Carben-Komplexe bereitzustellen, die den zuvor genannten Nachteilen abhelfen.The object was therefore to provide cationic carbene complexes which remedy the disadvantages mentioned above.
Demgemäß wurden neue dikationische Rutheniumkomplexe der allgemeinen Formel IAccordingly, new dicationic ruthenium complexes of the general formula I
Figure imgf000002_0001
Figure imgf000002_0001
gefunden, in welcherfound in which
R1, R2, R3, R4 unabhängig voneinander Wasserstoff, Ci- bis C 0-Alkyl, Cι~ bis C n-Halogenalkyl oder ein gegebenenfalls ein- bis fünffach durch Cι~ bis Cβ-Alkyl, Halogen und/oder Cyano substituiertes Aryl oder C - bis C2n-Aralkyl,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 unabhängig voneinander schwach oder nicht koordinierender, anionischer Rest L1, L2, L3 , L4, L5 unabhängig voneinander neutrale 2-Elektro- nendonor-Liganden oder zwei bzw. mehrere durch eine Brücke miteinander verbundene Chelat-LigandenX, 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
m, n unabhängig voneinander 0 oder 1.m, n independently of one another 0 or 1.
Die dikationischen Rutheniumkomplexe I können durch Umsetzung von kationischen Vinyl-Komplexen der Zusammensetzung [Ru(R1C=CR2R3)L1L2L3L ]X, deren Herstellung und die ihrer Edukte aus WO-A-99/58538, Organometallics 1998, Vol. 17, Seiten 3091 bis 3100, DE-A-198 00 934, Organometallics 1996, Vol. 15, Seiten 1960 bis 1962 und Organometallics 1997, Vol. 16, Seite 3867 bis 3869 bekannt sind, mit 0,9 bis 20 Moläquivalenten, bevorzugt 0,95 bis 5 Moläquivalenten, insbesondere 1 bis 3 Moläquivalenten einer Säure HY oder eines Alkylierungsmittels R4Y in organischen Lösungsmitteln unter Inertgasatmosphäre bei Temperaturen von (-100) bis (+200) °C, bevorzugt (-20) bis 100°C, besonders bevorzugt (-10) bis 80°C, insbesondere (-5) bis 30°C und einem Druck von 0,1 bis 20 bar, bevorzugt bei 0,5 bis 5 bar, besonders bevorzugt 0,8 bis 2 bar, insbesondere bei Normaldruck (Atmosphärendruck) erhalten werden. Die Reaktionszeiten betragen in der Regel 0,01 bis 20 h, bevorzugt 0,05 bis 10 h, insbesondere 0,05 bis 3 h. Als Reaktionsgefäße eignen sich in der Regel Glas- oder Stahlbehälter, die gegebenenfalls mit Keramik ausgekleidet sind.The dicationic ruthenium complexes I can be obtained by reacting cationic vinyl complexes of the composition [Ru (R 1 C = CR 2 R 3 ) L 1 L 2 L 3 L] X, their preparation and those of their starting materials from WO-A-99/58538 , Organometallics 1998, vol. 17, pages 3091 to 3100, DE-A-198 00 934, Organometallics 1996, vol. 15, pages 1960 to 1962 and Organometallics 1997, vol. 16, pages 3867 to 3869, with 0, 9 to 20 molar equivalents, preferably 0.95 to 5 molar equivalents, in particular 1 to 3 molar equivalents of an acid HY or an alkylating agent R 4 Y in organic solvents under an inert gas atmosphere at temperatures from (-100) to (+200) ° C, preferably (- 20) to 100 ° C, particularly preferably (-10) to 80 ° C, in particular (-5) to 30 ° C and a pressure of 0.1 to 20 bar, preferably at 0.5 to 5 bar, particularly preferably 0 , 8 to 2 bar, especially at normal pressure (atmospheric pressure) can be obtained. The reaction times are generally 0.01 to 20 h, preferably 0.05 to 10 h, in particular 0.05 to 3 h. Glass or steel containers, which are optionally lined with ceramics, are generally suitable as reaction vessels.
Weiterhin können die dikationischen Rutheniumkomplexe I durch Umsetzung von Carben-Komplexen der Zusammensetzung [RuZ (=CR1CR2R3R4)L1L2L3L4]X oder von Carbin-Komplexen der Zusam- mensetzung [RuRiZ ( ≡CCR2R3R4) L1L2L3L4] X, in der Z ein einfach negativ geladener koordinierender Ligand ist, die aus WO-A-99/58538 bekannt sind, mit einem oder mehr Moläquivalenten eines Salzes MY in organischen Lösungsmitteln unter Inertgasatmosphäre bei Temperaturen von (-100) bis (+200) °C, bevorzugt (-20) bis 100°C, besonders bevorzugt (-10) bis 80°C, insbesondere (-5) bis 30°C und einem Druck von 0,1 bis 20 bar, bevorzugt bei 0,5 bis 5 bar, besonders bevorzugt 0,8 bis 2 bar, insbesondere bei Normaldruck (Atmosphärendruck) erhalten werden.Furthermore, the dicationic ruthenium complexes I can be converted by reacting carbene complexes of the composition [RuZ (= CR 1 CR 2 R 3 R 4 ) L 1 L 2 L 3 L 4 ] X or carbine complexes of the composition [RuR i Z (≡CCR 2 R 3 R 4 ) L 1 L 2 L 3 L 4 ] X, in which Z is a single negatively charged coordinating ligand known from WO-A-99/58538, with one or more molar equivalents of a salt MY in organic solvents under an inert gas atmosphere at temperatures from (-100) to (+200) ° C, preferably (-20) to 100 ° C, particularly preferably (-10) to 80 ° C, in particular (-5) to 30 ° C and a pressure of 0.1 to 20 bar, preferably at 0.5 to 5 bar, particularly preferably 0.8 to 2 bar, in particular at normal pressure (atmospheric pressure).
Ferner können die dikationischen Rutheniumkomplexe I durch Umsetzung von Komplexen der Zusammensetzung [RuX1X2L1L2L3L4] , die aus Organometallics 1998, Vol. 17, Seiten 5190 bis 5196 bekannt sind, mit Vinyl-Grignard-Reagenzien R3R2C=CR1MgX oder anderen Vi- nyl-Metall-Reagenzien in organischen Lösungsmitteln unter Inert- gasatmosphäre bei Temperaturen von (-100) bis (+100) °C, bevorzugt 10 bis 50°C, besonders bevorzugt 20 bis 40°C, insbesondere bei Raumtemperatur und einem Druck von 0,5 bis 5 bar, bevorzugt 0,8 bis 2 bar, insbesondere bei Normaldruck (Atmosphärendruck) und anschließende Umsetzung mit einem oder mehr Moläquivalenten eines Salzes MY und einer Säure HY oder eines Alkylierungsmit- tels R4Y in organischen Lösungsmitteln unter Inertgasatmosphäre bei Temperaturen von 0 bis 100°C, bevorzugt 10 bis 50°C, besonders bevorzugt 20 bis 40°C, insbesondere bei Raumtemperatur und einem Druck von 0,5 bis 5 bar, bevorzugt 0,8 bis 2 bar, insbesondere bei Normaldruck (Atmosphärendruck) erhalten werden.Furthermore, the dicationic ruthenium complexes I can be obtained by reacting complexes of the composition [RuX 1 X 2 L 1 L 2 L 3 L 4 ], which are known from Organometallics 1998, Vol. 17, pages 5190 to 5196, with vinyl Grignard reagents R 3 R 2 C = CR 1 MgX or other vinyl metal reagents in organic solvents under an inert gas atmosphere at temperatures from (-100) to (+100) ° C, preferably 10 to 50 ° C, particularly preferably 20 to 40 ° C, especially at room temperature and a pressure of 0.5 to 5 bar, is preferred 0.8 to 2 bar, in particular at normal pressure (atmospheric pressure) and subsequent reaction with one or more molar equivalents of a salt MY and an acid HY or an alkylating agent R 4 Y in organic solvents under an inert gas atmosphere at temperatures from 0 to 100 ° C., preferably 10 to 50 ° C, particularly preferably 20 to 40 ° C, in particular at room temperature and a pressure of 0.5 to 5 bar, preferably 0.8 to 2 bar, in particular at normal pressure (atmospheric pressure).
Die hierbei erhaltenen dikationischen Rutheniumkomplexe I können in situ als Katalysatorsystem ohne Aktivierung oder mit einer Säure HY oder einem Alkylierungsmittel RY aktiviert eingesetzt werden oder isoliert unter Inertgasatmosphäre gelagert werden. Gegebenenfalls werden die dikationischen Rutheniumkomplexe I in isolierter Form eingesetzt.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.
Als organische Lösungsmittel eignen sich Kohlenwasserstoffe, beispielsweise C5- bis C o-Alkane wie n-Pentan, iso-Pentan, Pen- tan-Gemische, n-Hexan, iso-Hexan, Hexan-Gemische, n-Heptan, iso- Heptan, Heptan-Gemische, n-Octan, iso-Octan, Octan-Gemische, n- Nonan, iso-Nonan, Nonan-Gemische, n-Decan, iso-Decan, Decan-Ge- mische, n-Dodecan, iso-Dodecan, Dodecan-Gemische oder deren Gemische, Ether, beispielsweise Diarylether wie Diphenylether oder C3- bis C o~Dialkylether wie Dirnethylether, Methylethylether, Diethylether, Methyl-tert . -butylether oder deren Gemische, Alkohole, beispielsweise C3.- bis C2o~Alkanole wie Methanol, Ethanol, N-Propanol, Iso-Propanol, N-Butanol, Butanol-Isomerengemische oder deren Gemische, Ester, beispielsweise C- bis C2n-Carbonsäu - reester wie Ameisensäuremethylester, Essigsäuremethylester, Es- sigsäureethylester oder deren Gemische, halogenierte Kohlenwasserstoffe, beispielsweise Cι~ bis Cs-Chloralkane wie Methylenchlorid, Chloroform, Tetrachlorkohlenstoff oder deren Gemische, Carbonsäuren, beispielsweise Cι~ bis C o-Carbonsäuren wie Ameisensäure, Essigsäure, Propionsäure oder deren Gemische, Nitrile beispielsweise C - bis C o~Alkylnitrile wie Acetonitril oder Arylnitrile wie Benzonitril, Amine, beispielsweise Cχ~ bis C n-Alkylamine wie Methylamin, Di ethylamin, Methyl-ethylamin, Diethylamin oder deren Gemische, bevorzugt Methanol, Methylenchlorid, Acetonitril und Diethylether, besonders bevorzugt Methy- lenchlorid.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 tert. 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 such as benzonitrile, amines, for example Cχ ~ to C n-alkyl amines such as methylamine, diethylamine, methylethylamine, diethylamine or mixtures thereof, are preferred Methanol, methylene chloride, acetonitrile and diethyl ether, particularly preferably methylene chloride.
Als Inertgase eignen sich alle inerten Gase, beispielsweise- Stickstoff und Edelgase wie Argon, bevorzugt Argon. Als Kation M eignen sich Metallionen, wie einwertige Metallionen, beispielsweise Lithium, Natrium, Kalium, Caesium, Kupfer, Silber, Thallium, Phosphonium, Ammonium und Carbenium, bevorzugt Silber und Thallium, besonders bevorzugt Silber.All 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.
Als Grignard-Reagenzien R3R2C=CR1MgX eignen sich substituierte oder unsubstituierte Vinylmagnesiumhalogenide, bevorzugt substituierte oder unsubstituierte Vinylmagnesiumchloride und Vinylma- gnesiurαbromide wie Vinylmagnesiumchlorid, Vinylmagnesiumbromid oder 1-Propenylmagnesiumchlorid oder andere Vinyl-Metall-Reagenzien, beispielsweise Vinylzinnhalogenide, Vinyllithiumhaloge- nide, Vinyltitanhalogenide oder Vinylzirkonhalogenide wie Tetra- vinylzinn.Suitable Grignard reagents R 3 R 2 C = CR 1 MgX are substituted or unsubstituted vinyl magnesium halides, preferably substituted or unsubstituted vinyl magnesium chlorides and vinyl magnesium bromides such as vinyl magnesium chloride, vinyl magnesium bromide or 1-propenyl magnesium magnesium chloride or other vinyl halide, for example vinyl halide, vinyl halide, vinyl halide, for example vinyl halide, such as vinyl halide, vinyl halide, or vinyl halide, for example nides, vinyl titanium halides or vinyl zirconium halides such as tetravinyl tin.
Die Reste R1, R2, R3 , R4, X und Y sowie die Liganden L1, L2 , L3 , L4 und L5 sowie die Indizes m und n haben folgende Bedeutungen:The 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:
R1 , R2 , R3 , R4 unabhängig voneinander Wasserstoff, - Cι~ bis C 0-Alkyl, bevorzugt Cι~ bis Cs-Alkyl wie Methyl,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,
Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec'. -Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dirnethylpropyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, iso-Heptyl, n-Octyl, iso-Octyl, besonders bevor- zugt Ci- bis C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso- Propyl, n-Butyl, iso-Butyl, sec. -Butyl und tert.-Butyl, insbesondere Methyl und Ethyl,Ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec '. -Butyl, tert-butyl, n-pentyl, iso-pentyl, sec.-pentyl, neo-pentyl, 1,2-dirnethylpropyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso- Heptyl, n-octyl, iso-octyl, particularly preferably Ci to C 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert.- Butyl, especially methyl and ethyl,
Cχ~ bis Co-Halogenalkyl , bevorzugt Cι~ bis C4-Halogenalkyl , besonders bevorzugt Cι~ bis C4-Fluor-, Chlor- und/oder Brom- alkyl wie Fluormethyl, Difluormethyl, Trifluormethyl, Chlormethyl, Dichlormethyl, Trichlormethyl, Brommethyl, Dibrom- methyl, Tribrommethyl ,Cχ ~ to Co-haloalkyl, preferably Cι ~ to C 4 haloalkyl, particularly preferably Cι ~ to C 4 -fluoro, chloro and / or bromoalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, Dibromomethyl, tribromomethyl,
Aryl, wie Phenyl, 1-Naphthyl, 2-Naphthyl, 1-Anthryl, 2-Anthryl und 9-Anthryl, bevorzugt Phenyl, 1-Naphthyl und 2-Naphthyl, besonders bevorzugt Phenyl, durch Cι~ bis Cs-Alkyl, Halogen und/oder Cyano ein- bis fünffach substituiertes Aryl, bevorzugt durch Cι~ bis C -Al - kyl, Fluor, Chlor, Brom und/oder Cyano ein- bis dreifach substituiertes Phenyl, besonders bevorzugt durch Methyl, Ethyl, Fluor, Chlor und/oder Cyano ein- bis dreifach substituiertes Phenyl wie 2-Methylphenyl, 3-Methylphenyl, 4-Me- thylphenyl, 2,4-Dimethylphenyl, 2, 5-Dimethylphenyl, 2,6-Di- methylphenyl, 3 , 4-Dimethylphenyl, 3 , 5-Dimethylphenyl , 2, 3,4-Trimethylphenyl, 2, 3, 5-Trimethylphenyl, 2,3,6-Trime- thylphenyl, 2, 4, 6-Trimethylphenyl, 2-Ξthylphenyl, 3-Ethyl- phenyl, 4-Ethylphenyl, 2-Fluorphenyl, 3-Fluorphenyl, 4-Flu- orphenyl, 2,4-Difluorphenyl, 2, 5-Difluorphenyl, 2,6-Difluor- phenyl, 3, 4-Difluorphenyl, 3 , 5-Difluorphenyl, 2, 3 ,4-Trifluorphenyl, 2, 3, 5-Trifluorphenyl, 2, 3, 6-Trifluorphenyl, 2, 4, 6-Trifluorphenyl, 2-Chlorphenyl, 3-Chlorphenyl, 4-Chlor- phenyl, 2, 4-Dichlorphenyl, 2, 5-Dichlorphenyl, 2,6-Dichlor- phenyl, 3, 4-Dichlorphenyl, 3 , 5-Dichlorphenyl, 2,3,4-Trich- lorphenyl, 2,3, 5-Trichlorphenyl , 2,3, 6-Trichlorphenyl, 2,4, 6-Trichlorphenyl, 2-Chlor-4-methylphenyl, 2-Chlor-5-me- thylphenyl, 2-Fluor-6-methylphenyl, 3-Cyano-4-chlorphenyl, 3Cyano-5-fluorpheny1 , - C7- bis C20-Aralkyl, bevorzugt C7- bis Cι -Phenylalkyl wieAryl, 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-dimethylphenyl, 3, 5-dimethylphenyl, 2, 3,4-trimethylphenyl, 2, 3, 5-trimethylphenyl, 2,3,6-trimethylphenyl, 2, 4, 6-trimethylphenyl, 2-Ξthylphenyl, 3-ethylphenyl, 4- Ethylphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 2, 5-difluorophenyl, 2,6-difluoro- phenyl, 3, 4-difluorophenyl, 3, 5-difluorophenyl, 2, 3, 4-trifluorophenyl, 2, 3, 5-trifluorophenyl, 2, 3, 6-trifluorophenyl, 2, 4, 6-trifluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2, 4-dichlorophenyl, 2, 5-dichlorophenyl, 2,6-dichlorophenyl, 3, 4-dichlorophenyl, 3, 5-dichlorophenyl, 2,3,4-trich- lorphenyl, 2,3,5-trichlorophenyl, 2,3,6-trichlorophenyl, 2,4,6-trichlorophenyl, 2-chloro-4-methylphenyl, 2-chloro-5-methylphenyl, 2-fluoro-6- methylphenyl, 3-cyano-4-chlorophenyl, 3cyano-5-fluoropheny1, - C 7 - to C 20 -aralkyl, preferably C 7 - to -C -phenylalkyl such as
Benzyl, 1-Phenethyl, 2-Phenethyl, 1-Phenyl-propyl, 2-Phenyl- propyl, 3-Phenyl-propyl, 1-Phenyl-butyl, 2-Phenyl-butyl, 3-Phenyl-butyl und 4-Phenyl-butyl, besonders bevorzugt Benzyl, 1-Phenethyl und 2-Phenethyl, insbesondere Benzyl, - durch Cι~ bis Cs-Alkyl, Halogen und/oder Cyano ein- bis fünffach substituiertes Aralkyl, bevorzugt durch Cι~ bis C - Alkyl, Fluor, Chlor, Brom und/oder Cyano ein- bis dreifach substituiertes Benzyl, besonders bevorzugt durch Methyl, Ethyl, Fluor, Chlor und/oder Cyano ein- bis dreifach substi- tuiertes Benzyl wie 2-Methylbenzyl, 3-Methylbenzyl, 4-Me- thylbenzyl, 2, 4-Dimethylbenzyl, 2 , 5-Dimethylbenzyl, 2,6-Di- methylbenzyl , 3 , 4-Dimethylbenzyl , 3 , 5-Dimethylbenzyl , 2 , 3 , 4-Trimethylbenzyl, 2 , 3 , 5-Trimethylbenzyl, 2,3,6-Trime- thylbenzyl, 2, 4, 6-Trimethylbenzyl, 2-Ethylbenzyl, 3-Ethyl- benzyl, 4-Ethylbenzyl, 2-Fluorbenzyl, 3-Fluorbenzyl, 4-Flu- orbenzyl, 2 , 4-Difluorbenzyl, 2 , 5-Difluorbenzyl , 2, 6-Difluorbenzyl, 3 , 4-Difluorbenzyl, 3 , 5-Difluorbenzyl, 2 , 3 , 4-Trifluorbenzyl, 2, 3 , 5-Trifluorbenzyl, 2 , 3 , 6-Trifluorbenzyl , 2, 4, 6-Trifluorbenzyl, 2-Chlorbenzyl, 3-Chlorbenzyl, 4-Chlor- benzyl, 2, 4-Dichlorbenzyl, 2, 5-Dichlorbenzyl, 2,6-Dichlor- benzyl, 3, 4-Dichlorbenzyl, 3 , 5-Dichlorbenzyl, 2,3,4-Trich- lorbenzyl, 2 , 3 , 5-Trichlorbenzyl, 2, 3 , 6-Trichlorbenzyl, 2, 4, 6-Trichlorbenzyl, 2-Chlor-4-methylbenzyl, 2-Chlor-5-me- thylbenzyl, 2-Fluor-6-methylbenzyl, 3-Cyano-4-chlorbenzyl, 3-Cyano-5-fluorbenzyl,Benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl- butyl, particularly preferably benzyl, 1-phenethyl and 2-phenethyl, in particular benzyl, - by Cι ~ to Cs-alkyl, halogen and / or cyano mono- to pentasubstituted aralkyl, preferably by Cι ~ to C - alkyl, fluorine, chlorine , Bromine and / or cyano monosubstituted to trisubstituted benzyl, particularly preferably benzyl monosubstituted to trisubstituted by methyl, ethyl, fluorine, chlorine and / or cyano, such as 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2, 4-dimethylbenzyl, 2, 5-dimethylbenzyl, 2,6-dimethylbenzyl, 3, 4-dimethylbenzyl, 3, 5-dimethylbenzyl, 2, 3, 4-trimethylbenzyl, 2, 3, 5-trimethylbenzyl, 2, 3,6-trimethylbenzyl, 2, 4, 6-trimethylbenzyl, 2-ethylbenzyl, 3-ethylbenzyl, 4-ethylbenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2, 4-difluorobenzyl, 2, 5-difluorobenzyl, 2, 6-difluorobenzyl, 3, 4-difluorobenzyl, 3, 5- Difluorobenzyl, 2, 3, 4-trifluorobenzyl, 2, 3, 5-trifluorobenzyl, 2, 3, 6-trifluorobenzyl, 2, 4, 6-trifluorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2, 4-dichlorobenzyl, 2, 5-dichlorobenzyl, 2,6-dichlorobenzyl, 3, 4-dichlorobenzyl, 3, 5-dichlorobenzyl, 2,3,4-trichlorobenzyl, 2, 3, 5-trichlorobenzyl, 2, 3, 6-trichlorobenzyl, 2, 4, 6-trichlorobenzyl, 2-chloro-4-methylbenzyl, 2-chloro-5-methylbenzyl, 2-fluoro-6-methylbenzyl, 3-cyano-4-chlorobenzyl, 3- cyano-5-fluorobenzyl,
X, Y unabhängig voneinander schwach oder nicht koordinierende, anionische Reste beispielsweise Phosphate, Sulfate, Borate, Perchlorate und Sul- fonate, bevorzugt PF5, BF4, B[C6H5]4, B[C6F5]4,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 ,
B [CgH3 (mCF3)2] 4, C104, SO4, CF3S03 oder FS03, besonders bevorzugt BF4 oder B[C6H3 (mCF3) 2]4,B [CgH 3 (mCF 3 ) 2 ] 4 , C10 4 , SO 4 , CF 3 S0 3 or FS0 3 , particularly preferably BF 4 or B [C 6 H 3 (mCF 3 ) 2 ] 4 ,
L1, L2 , L3 , L , L5 unabhängig voneinander - neutrale 2-Elektronendonor-Liganden z.B. Amine wie primäre Amine, sekundäre Amine, tertiäre Amine, beispielsweise Trimethylamin oder Tetramethylendiamin, Nitrile wie Acetoni- tril oder Benzonitril, bevorzugt CH3CN, Aromaten, beispielsweise Benzol, Toluol oder Xylole, aromatische Carbonsäuren wie Pikrinsäure, Ketone, beispielsweise Aceton, Aldehyde, Ammoniak, Wasser, Kohlenmonoxid, Phosphane wie Phosphane mit aliphatischen, aliphatisch-aromatischen oder aromatischen Substituenten, beispielsweise P (iso-Propyl) 3, P(Cyclohe- xyl)3, P(CH3)2(C6H5) , P (CH3) (C6H5) 2, P(C6H5)3 oder H3C-C[CH2-P(CSH5)2]3, Arsane wie As (CH3) 2 (C6H5) , As (CH3) (C6H5) oder As(CgH5)3, acyclische oder cyclische Diene, beispiels- weise acyclische oder cyclische C4- bis Cι6-Diene wie Cyclo- pentadien, Stibane sowie Carbenoide mit Heterosubstitution, zwei bzw. mehrere durch eine Brücke miteinander verbundene Chelat-Liganden wie α- und ß-Hydroxycarbonylverbindungen (Hydroxycarbonsäuren, Hydroxyketone, Hydroxyaldehyde, enoli- sierbare Diketone, z.B. Acetylaceton {2, 4-Pentandion} , Dia- ine wie Tetramethylendiamin, Triamine, Tetramine, Diole wie 1, 3-Propandiol, Triole, Aminoalkohole, Polyoxycarbonsäuren wie Ethylendiamintetraessigsäure oder Nitrilotriessigsäure, Polyamine sowie Chelatphosphane wie Diphenylphosphinoethan, Diphenylphosphinomethan oder alkylsubstituierte Chelatphosphane, beispielsweise durch C±- bis C4~Alkyl ein- bis zwanzigfach substituierte Chelatphosphane,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 6 H 5 ) 3 or H 3 CC [CH 2 -P (C S H 5 ) 2 ] 3 , arsanes such as As (CH 3 ) 2 (C 6 H 5 ), As (CH 3 ) (C 6 H 5 ) or As (CgH 5 ) 3 , acyclic or cyclic dienes, for example acyclic or cyclic C 4 - to C 6 -dienes such as cyclopentadiene, stibans and carbenoids with hetero substitution, two or more chelate ligands connected to one another by a bridge, such as α- and ß -Hydroxycarbonyl compounds (hydroxycarboxylic acids, hydroxyketones, hydroxyaldehydes, enolizable diketones, for example acetylacetone {2, 4-pentanedione}, diamines such as tetramethylene diamine, triamines, Te tramine, diols such as 1, 3-propanediol, triols, amino alcohols, polyoxycarboxylic acids such as ethylenediaminetetraacetic acid or nitrilotriacetic acid, polyamines and chelate phosphines such as diphenylphosphinoethane, diphenylphosphinomethane or alkyl-substituted chelate phosphines, for example substituted by C 1- to C 4 -phosphate,
m und n unabhängig voneinander - die Zahlen 0 oder 1, bevorzugt m=0 und n=l.m and n independently of one another - the numbers 0 or 1, preferably m = 0 and n = 1.
Insbesondere bedeutet R1 Wasserstoff.In particular, R 1 is hydrogen.
Die Liganden L1 und L2 haben insbesondere folgende Bedeutungen: L1, L2 unabhängig voneinanderThe ligands L 1 and L 2 have in particular the following meanings: L 1 , L 2 independently of one another
P (iso-Propyl) 3 oder P (Cyclohexyl) 3,P (iso-propyl) 3 or P (cyclohexyl) 3 ,
L3, L4 L 3 , L 4
CH3CN.CH 3 CN.
Dieser Katalysatoren eignen sich für chemische Reaktionen wie Hydrierungen und Additionsreaktionen wie Additionen von CHC13 an Olefine, insbesondere für Metathesereaktionen von Olefinen, wie Selbstmetathese eines Olefins oder Kreuzmetathese zweier oder mehrerer Olefine, ringöffnende Metathesepolymerisation (ROMP) von cyclischen Olefinen, selektive Ringöffnung von cyclischen Olefinen mit acyclischen Olefinen, acyclische Dien-Metathesepo- lymerisation (ADMET) , Ringschlußmetathese (RCM) und weitere neuartige Metathesevarianten. BeispieleThese 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. Examples
Synthese kationischer Vinyl-KomplexeSynthesis of cationic vinyl complexes
Beispiel 1example 1
Herstellung von [Ru (CH=CH2) (MeCN) 2 (P (-Cyclohexyl) 3) 2] CIPreparation of [Ru (CH = CH 2 ) (MeCN) 2 (P (-cyclohexyl) 3 ) 2 ] CI
Zu einer Lösung von 259 mg (0,36 mmol) [RuHCl (=C=CH2) (P (-Cyclo - hexyl)3) ] in 15 ml Methylenchlorid wurden bei RaumtemperaturA solution of 259 mg (0.36 mmol) [RuHCl (= C = CH 2 ) (P (-cyclo-hexyl) 3 )] in 15 ml of methylene chloride was added at room temperature
10 ml Acetonitril gegeben. Nach Entfernen des Lösungsmittels wurde der Rückstand dreimal mit je 8 ml Pentan gewaschen und i.Given 10 ml of acetonitrile. After removing the solvent, the residue was washed three times with 8 ml of pentane and i.
Vak. getrocknet. Ausbeute: 251 mg (86%) ; Schmelzpunkt: 78°CVak. dried. Yield: 251 mg (86%); Melting point: 78 ° C
(Zers.) .(Dec.).
Beispiel 2Example 2
Herstellung von [Ru (CH=CH2) (MeCN) 2 (P (-Cyclohexyl) 3) 2] PF6 Preparation of [Ru (CH = CH 2 ) (MeCN) 2 (P (-cyclohexyl) 3 ) 2 ] PF 6
Zu einer Lösung von 270 mg (0,39 mmol) [RuHCl (=C=CH2) (P (-Cyclo - hexyl)3)2] in 15 ml Methylenchlorid und 15 ml Acetonitril wurden bei Raumtemperatur 250 mg (1,36 mmol) KPFß gegeben, 35 min gerührt und anschließend das Lösungsmittel entfernt. Der Rückstand wurde nacheinander mit 12 ml und 7 ml Methylenchlorid extra- hiert, das Lösungsmittels entfernt, der Rückstand zweimal je mit 8 ml Pentan gewaschen und i. Vak. getrocknet. Ausbeute: 307 mg (87%); Schmelzpunkt: 55°C (Zers.).To a solution of 270 mg (0.39 mmol) [RuHCl (= C = CH 2 ) (P (-cyclo-hexyl) 3 ) 2 ] in 15 ml methylene chloride and 15 ml acetonitrile was added 250 mg (1.36 mmol) KPF ß added, stirred for 35 min and then the solvent removed. The residue was extracted successively with 12 ml and 7 ml of methylene chloride, the solvent was removed, the residue was washed twice with 8 ml each of pentane and i. Vak. dried. Yield: 307 mg (87%); Melting point: 55 ° C (dec.).
Beispiel 3Example 3
Herstellung von [Ru(CH=CH2) (MeCN) 2 (P (-Cyclohexyl) 3) 2] B (-Phenyl)Preparation of [Ru (CH = CH 2 ) (MeCN) 2 (P (-cyclohexyl) 3 ) 2 ] B (-phenyl)
Zu einer Lösung von 450 mg (0,49 mmol) [Ru (CH=CH2) (MeCN) 2 (P (-Cyclohexyl) 3) ] PF6 in 20 ml Methanol wurden bei Raumtemperatur 200 mg (0,58 mmol) NaB (-Phenyl) 4 gegeben. Nach 15 min Rühren bei Raumtemperatur wurde der Niederschlag abfiltriert, dreimal mit je 10 ml Methanol gewaschen und i. Vak. getrocknet. Ausbeute: 416 mg (78%); Schmelzpunkt: 100°C (Zers.).To a solution of 450 mg (0.49 mmol) [Ru (CH = CH 2 ) (MeCN) 2 (P (-cyclohexyl) 3 )] PF 6 in 20 ml methanol was added 200 mg (0.58 mmol) Given NaB (-phenyl) 4 . After stirring for 15 min at room temperature, the precipitate was filtered off, washed three times with 10 ml of methanol each time and i. Vak. dried. Yield: 416 mg (78%); Melting point: 100 ° C (dec.).
Beispiel 4Example 4
Herstellung von [Ru (CH=CH2) (MeCN) 2 (P (-Cyclohe - xyl)3)2]B[C6H3(mCF3)2]4 Preparation of [Ru (CH = CH 2 ) (MeCN) 2 (P (-cyclohexyl) 3 ) 2 ] B [C 6 H 3 (mCF 3 ) 2 ] 4
Eine Suspension von 54 mg (0,06 mmol) [Ru (CH=CH2) (MeCN) 2 (P (-Cyclohexyl) 3) 2] PF6 in 10 ml Diethylether wurde bei 0°C mit einer Lösung von 55 mg (0,06 mmol) NaB [C6H3 (mCF3) ] 4 in 15 ml Diethyle- ther versetzt, 10 min gerührt und filtriert wird. Aus dem Fil- trat wurde das Lösungsmittel entfernt und der Rückstand dreimal mit je 5 ml Pentan gewaschen und i. Vak. getrocknet. Ausbeute: 94 mg (97 %) ; Schmelzpunkt: 70°C (Zers.).A suspension of 54 mg (0.06 mmol) of [Ru (CH = CH 2 ) (MeCN) 2 (P (-cyclohexyl) 3 ) 2 ] PF 6 in 10 ml of diethyl ether was added at 0 ° C. with a solution of 55 mg (0.06 mmol) NaB [C 6 H 3 (mCF 3 )] 4 in 15 ml diethyl ether is added, the mixture is stirred for 10 min and filtered. The solvent was removed from the filtrate and the residue was washed three times with 5 ml each of pentane and i. Vak. dried. Yield: 94 mg (97%); Melting point: 70 ° C (decomp.).
Beispiel 5Example 5
Herstellung von [Ru (CH=CHPhenyl) (MeCN) 3 (P (-iso-propyl) 3) 2] CIPreparation of [Ru (CH = CHPhenyl) (MeCN) 3 (P (-isopropyl) 3 ) 2 ] CI
Zu einer Lösung von 81 mg (0,14 mmol) [RuHCl (=C=CHPhe- nyl) (P (-iso-Propyl) 3) ] in 8 ml Methylenchlorid wurden bei Raumtemperatur 3 ml Acetonitril gegeben. Nach Entfernung des Lösungsmittels wurde der Rückstand dreimal mit je 5 ml Pentan gewaschen und i. Vak. getrocknet. Ausbeute: 87 mg (93%); Schmelz- punkt: 59°C (Zers.).To a solution of 81 mg (0.14 mmol) [RuHCl (= C = CHPhenyl) (P (-isopropyl) 3 )] in 8 ml methylene chloride was added 3 ml acetonitrile at room temperature. After removal of the solvent, the residue was washed three times with 5 ml of pentane and i. Vak. dried. Yield: 87 mg (93%); Melting point: 59 ° C (dec.).
Beispiel 6Example 6
Herstellung von [Ru (CH=CHPhenyl) (MeCN) 3 (P (-iso-Propyl) 3) 2] PF6 Preparation of [Ru (CH = CHPhenyl) (MeCN) 3 (P (-isopropyl) 3 ) 2 ] PF 6
Zu einer Lösung von 85 mg (0,12 mmol) [Ru (CH=CHPhe- nyl) (MeCN) (P (-iso-propyl) 3) ] CI in 5 ml Methylenchlorid und 3 ml Acetonitril wurden bei Raumtemperatur 150 mg (0,81 mmol) KPFδ gegeben. Nach 30 min Rühren wurde das Lösungsmittel entfernt und der Rückstand nacheinander mit 8 ml und 5 ml Methylenchlorid extrahiert. Nach Entfernen des Lösungsmittels wurde der Feststoff zweimal mit je 5 ml Pentan gewaschen und i. Vak. getrocknet. Ausbeute: 73 mg (75%); Schmelzpunkt: 36°C (Zers.).To a solution of 85 mg (0.12 mmol) [Ru (CH = CHPhenyl) (MeCN) (P (-isopropyl) 3 )] CI in 5 ml methylene chloride and 3 ml acetonitrile was added 150 mg at room temperature ( Given 0.81 mmol) KPF δ . After stirring for 30 min, the solvent was removed and the residue was extracted successively with 8 ml and 5 ml of methylene chloride. After removing the solvent, the solid was washed twice with 5 ml of pentane and i. Vak. dried. Yield: 73 mg (75%); Melting point: 36 ° C (dec.).
Beispiel 7Example 7
Herstellung von [Ru (CH=CHPhenyl) (MeCN) 3 (P (-iso-Propyl) 3) 2] B (-Phe - nyl) 4 Preparation of [Ru (CH = CHPhenyl) (MeCN) 3 (P (-isopropyl) 3 ) 2 ] B (-Phenyl) 4
Zu einer Lösung von 230 mg (0,23 mmol) [Ru (CH=CHPhe- nyl) (MeCN) 3 (P (-iso-Propyl) 3) 2] PF6 in 15 ml Methanol wurden bei Raumtemperatur 200 mg (0,58 mmol) NaBPhenyl4 gegeben. Nach 15 min Rühren bei Raumtemperatur wurde der Niederschlag abfiltriert, dreimal mit je 10 ml Methanol gewaschen und i. Vak. ge- trocknet. Ausbeute: 162 mg (74%); Schmelzpunkt: 114°C (Zers.). Beispiel 8To a solution of 230 mg (0.23 mmol) [Ru (CH = CHPhenyl) (MeCN) 3 (P (-isopropyl) 3 ) 2 ] PF 6 in 15 ml of methanol were 200 mg at room temperature (0 , 58 mmol) of NaBPhenyl 4 . After stirring for 15 min at room temperature, the precipitate was filtered off, washed three times with 10 ml of methanol each time and i. Vak. dried. Yield: 162 mg (74%); Melting point: 114 ° C (dec.). Example 8
Herstellung von [Ru (CH=CHPh) (MeCN) 3 (P (-iso-Pro - pyl) 3) 2] B [C6H3 (mCF3) 2] 4 Preparation of [Ru (CH = CHPh) (MeCN) 3 (P (-iso-Propyl) 3 ) 2 ] B [C 6 H 3 (mCF 3 ) 2 ] 4
Eine Suspension von 73 mg (0,092 mmol)A suspension of 73 mg (0.092 mmol)
[Ru(CH=CHPh) (MeCN) 3 (P (-iso-Propyl) 3)2] PF5 in 15 ml Diethylether wurde bei 0°C mit einer Lösung von 77 mg (0,087 mmol) NaB [C6H3 (mCF3) 234 in 20 ml Diethylether versetzt und nach 10 min Rühren die entstandene Lösung filtriert. Aus dem Filtrat wurde das Lösungsmittel entfernt und der Rückstand dreimal mit je 5 ml Pentan gewaschen und i. Vak. getrocknet. Ausbeute: 83 mg[Ru (CH = CHPh) (MeCN) 3 (P (-isopropyl) 3 ) 2 ] PF 5 in 15 ml diethyl ether was treated at 0 ° C with a solution of 77 mg (0.087 mmol) NaB [C 6 H 3 (mCF 3 ) 2 3 4 in 20 ml of diethyl ether and, after stirring for 10 min, the resulting solution is filtered. The solvent was removed from the filtrate and the residue was washed three times with 5 ml each of pentane and i. Vak. dried. Yield: 83 mg
(63 %) ; Schmelzpunkt: 100°C (Zers.).(63%); Melting point: 100 ° C (dec.).
Herstellung dikationischer Carben-KomplexeProduction of dicationic carbene complexes
Beispiel 9Example 9
Herstellung von [Ru(=CHCH3) (MeCN) 2 (PCy3) 2] (PF5)X, (BF4)2_X Preparation of [Ru (= CHCH 3 ) (MeCN) 2 (PCy 3 ) 2 ] (PF 5 ) X , (BF 4 ) 2 _ X
Eine Lösung von 118 mg (0,13 mmol) [Ru (CH=CH2) (MeCN) 2 (P (-Cyclo - hexyl) 3) ] PF6 in 10 ml Methylenchlorid wurde bei Raumtemperatur mit einem Überschuß einer Lösung von HBF4 (2,08 mmol) in Diethylether (1,3 ml einer 1,6 molaren Lösung von HBF4 in Diethyle- ther) versetzt. Nach 2 min wurde das Lösungsmittel entfernt, der Rückstand mit 15 ml Pentan gewaschen und i. Vak. getrocknet. Ausbeute: 120 mg (0,12 mmol für x=l, 86 %) , Schmelzpunkt: 49°C (Zers . ) .A solution of 118 mg (0.13 mmol) [Ru (CH = CH 2 ) (MeCN) 2 (P (-cyclo-hexyl) 3 )] PF 6 in 10 ml methylene chloride was added at room temperature with an excess of a solution of HBF 4 (2.08 mmol) in diethyl ether (1.3 ml of a 1.6 molar solution of HBF 4 in diethyl ether) was added. After 2 min the solvent was removed, the residue was washed with 15 ml of pentane and i. Vak. dried. Yield: 120 mg (0.12 mmol for x = 1.86%), melting point: 49 ° C. (dec.).
Beispiel 10Example 10
Herstellung von [Ru(=CHCH3) (MeCN) 2 (P (-Cyclohexyl) 3)2] (B (-Phenyl) 4) x, (BF4)2_X Preparation of [Ru (= CHCH 3 ) (MeCN) 2 (P (-cyclohexyl) 3 ) 2 ] (B (-phenyl) 4) x, (BF 4 ) 2 _ X
Eine Lösung von 153 mg (0,14 mmol) [Ru (CH=CH2) (MeCN) 2 (P (-Cyclo - hexyl) 3) 2] B (-Phenyl) 4 in 12 ml Methylenchlorid wurde bei Raumtemperatur mit einem Überschuß einer Lösung von HBF4 (3,2 mmol) in Diethylether (2,0 ml einer 1,6 molaren Lösung von HBF4 in Diethylether) versetzt. Nach 2 min wurde das Lösungsmittel ent- fernt, der Rückstand zweimal mit je 8 ml Pentan gewaschen und i. Vak. getrocknet. Ausbeute: 157 mg.A solution of 153 mg (0.14 mmol) [Ru (CH = CH 2 ) (MeCN) 2 (P (-Cyclo - hexyl) 3 ) 2 ] B (-phenyl) 4 in 12 ml methylene chloride was washed at room temperature with a Excess of a solution of HBF 4 (3.2 mmol) in diethyl ether (2.0 ml of a 1.6 molar solution of HBF 4 in diethyl ether) was added. After 2 min the solvent was removed, the residue was washed twice with 8 ml each of pentane and i. Vak. dried. Yield: 157 mg.
1H-NMR (CD2C12, 200 MHz): δ = 17.58 [q, J(HH) = 5.8 Hz, 1 H, CHCH3] , 2.96 [d, 1 H, J(HH) = 5.8 Hz, CHCH3] , 2.83 (s, 6H, CH3CN) , 2.55-1.31 (je m, 66 H, C6Hn) . Beispiel 111H-NMR (CD 2 C1 2 , 200 MHz): δ = 17.58 [q, J (HH) = 5.8 Hz, 1 H, CHCH 3 ], 2.96 [d, 1 H, J (HH) = 5.8 Hz, CHCH 3 ], 2.83 (s, 6H, CH 3 CN), 2.55-1.31 (each m, 66 H, C 6 Hn). Example 11
Herstellung von [Ru (=CHCH3) (MeCN) 2 (P (-Cyclohe - xyl) 3)2] [B [C6H3 (mCF3) 2] 4] 2 Preparation of [Ru (= CHCH 3 ) (MeCN) 2 (P (-cyclohexyl) 3 ) 2 ] [B [C 6 H 3 (mCF 3 ) 2 ] 4 ] 2
Eine rote Lösung von 94 mg (0,058 mmol)A red solution of 94 mg (0.058 mmol)
[Ru(CH=CH2) (MeCN) 2(P (-Cyclohexyl) 3)2]B[C6H3 (mCF3) 2] 4 in 8 ml Me¬ thylenchlorid wurde bei 0°C mit einer Lösung von 58 mg (0,057 mmol) [H(0(C2H5)2) 2]B[C6H3 (mCF3)2] 4 in 4 ml Methylenchlorid ver- setzt. Nach Entfernen des Lösungsmittels wurde der Feststoff dreimal mit je 5 ml Pentan gewaschen und i. Vak. getrocknet. Ausbeute: 130 mg (91 %) ; Schmelzpunkt: 130°C (Zers.).[Ru (CH = CH 2) (MeCN) 2 (P (cyclohexyl) 3) 2] B [C 6 H 3 (m CF 3) 2] 4 in 8 mL of Me ¬ thylenchlorid at 0 ° C with a solution of 58 mg (0.057 mmol) [H (0 (C 2 H 5 ) 2 ) 2 ] B [C 6 H 3 (mCF 3 ) 2 ] 4 in 4 ml methylene chloride. After removing the solvent, the solid was washed three times with 5 ml of pentane and i. Vak. dried. Yield: 130 mg (91%); Melting point: 130 ° C (dec.).
1H-NMR (CD2C12, 400 MHz): δ = 17.20 [q, J(HH) = 5.9 Hz, 1 H, CHCH3] , 7.72 [s, 16 H, o-H von B [C6H3 (mCF3) 2] 4] , 7.57 [s, 8 H, p-H von B[CeH3 (mCF3)2] ] , 2.87 [d, J(HH) = 5.9 Hz, 3 H, CHCH3] , 2.75 (s, 6H, CH3CN) , 2.17, 1.96-1.73, 1.35-1-23 (je m, 66 H, CsHu) .1H-NMR (CD 2 C1 2 , 400 MHz): δ = 17.20 [q, J (HH) = 5.9 Hz, 1 H, CHCH 3 ], 7.72 [s, 16 H, oH of B [C 6 H 3 ( mCF 3 ) 2 ] 4 ], 7.57 [s, 8 H, pH of B [C e H 3 (mCF 3 ) 2 ]], 2.87 [d, J (HH) = 5.9 Hz, 3 H, CHCH 3 ], 2.75 (s, 6H, CH 3 CN), 2.17, 1.96-1.73, 1.35-1-23 (each m, 66 H, C s Hu).
Beispiele zur MetatheseExamples of metathesis
Beispiel 12Example 12
Ringöffnende Metathesepolymerisation von Cycloocten mit [Ru(CH2=CH2) (MeCN) 2 ( (-Cyclohexyl) 3) 2] [PF6] / HBFRing opening metathesis polymerization of cyclooctene with [Ru (CH 2 = CH 2 ) (MeCN) 2 ((-Cyclohexyl) 3 ) 2 ] [PF 6 ] / HBF
Eine Lösung von 55 mg [Ru(CH2=CH2) (MeCN) 2 (PCy3) 2] [PFg] in 3 ml Methylenchlorid wurde zu einer Lösung von 0,5 ml HBF4 in 10 ml Cycloocten gegeben. Nach 45 min war die Mischung erstarrt. Die Aufarbeitung nach 18 h erfolgte durch Lösen des Polymers inA solution of 55 mg [Ru (CH 2 = CH 2 ) (MeCN) 2 (PCy 3 ) 2 ] [PFg] in 3 ml methylene chloride was added to a solution of 0.5 ml HBF 4 in 10 ml cyclooctene. After 45 minutes the mixture had solidified. Working up after 18 h was carried out by dissolving the polymer in
300 ml Methylenchlorid bei 40°C und erneutes Ausfällen des Polymers durch Eingießen der Lösung in kaltes Methanol. Man erhielt 8,1 g Polycycloocten (Ausbeute 96 %) mit einem trans-Anteil von ca. 48% gemäß NMR-Messung.300 ml of methylene chloride at 40 ° C and the polymer precipitates again by pouring the solution into cold methanol. 8.1 g of polycyclooctene (yield 96%) with a trans content of approximately 48% were obtained by NMR measurement.
Beispiel 13Example 13
Metathese von 1-Octen mit [Ru (CH2=CH2) (MeCN) 2 (P (-Cyclohe xyl) 3) 2] CPF6] / HBF4 Metathesis of 1-octene with [Ru (CH 2 = CH 2 ) (MeCN) 2 (P (-cyclohexyl) 3) 2] CPF 6 ] / HBF 4
Eine Lösung von 30 mg [Ru (CH=CH2) (MeCN) 2 (P (-Cyclohexyl) 3) 2] [PF6] in 3 ml Methylenchlorid wurde mit 5 ml 1-Octen versetzt und bei Raumtemperatur gerührt. Nach 15 h waren nach GC/MS-Analyse (GCD- Gerät von HP, Säule HP-5, Länge 30 cm, 0=0,25 mm, ID=lμm) haupt- sächlich Cχ2- und Cι4-01efine entstanden. Cι3-01efine konnten nicht detektiert werden. A solution of 30 mg [Ru (CH = CH 2 ) (MeCN) 2 (P (-cyclohexyl) 3) 2 ] [PF 6 ] in 3 ml methylene chloride was mixed with 5 ml 1-octene and stirred at room temperature. After 15 h, according to GC / MS analysis (GCD device from HP, column HP-5, length 30 cm, 0 = 0.25 mm, ID = 1 μm), mainly Cχ 2 - and Cι 4 -01efins were formed. Cι 3 -01efine could not be detected.

Claims

Patentansprücheclaims
Dikationische Rutheniumkomplexe der allgemeinen Formel IDicationic ruthenium complexes of the general formula I
Figure imgf000012_0001
Figure imgf000012_0001
in derin the
Rl , R2 , R3 , R4 unabhängig voneinander Wasserstoff , Cι~ bis C 0 -Alkyl , Cι~ bis C o~Halogenalkyl oder ein gegebenenfalls ein- bis fünffach durch Cχ~ bis Cs-Alkyl , Halogen und/oder Cyano substi tuiertes Aryl oder C - bis C2o_Aralkyl ,R l , R 2 , R 3 , R 4 independently of one another are hydrogen, C 1 -C 8 -alkyl, C 1 -C 6 -haloalkyl or an optionally one to five times by C 1 -C 4 -alkyl, halogen and / or cyano substituted aryl or C - to C 2 o _ aralkyl,
X, Y unabhängig voneinander schwach oder nicht koordinierender, anionischer RestX, Y independently weak or non-coordinating anionic radical
L1 , L2 , 1_3 , L , L5 unabhängig voneinander neutrale 2-Elektro- nendonor-Liganden oder zwei bzw. mehrere durch eine Brücke miteinander verbundene Chelat-LigandenL 1 , L 2 , 1_3, L, 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,m unabhängig voneinander 0 oder 1.n, m independently of one another 0 or 1.
Dikationische Rutheniumkomplexe der allgemeinen Formel I nach Anspruch 1, dadurch gekennzeichnet, daßDicationic ruthenium complexes of the general formula I according to claim 1, characterized in that
R!,R2,R3,R4 unabhängig voneinander Wasserstoff, Methyl oder Phenyl,R !, R 2 , R 3 , R 4 independently of one another are hydrogen, methyl or phenyl,
X, Y PF6 , BF4 , B [C6H5_ 4 , B [C6F5] , B [C6H3 (mCF3 ) 2] 4 , C10 , S04 , CF3S03 oder FS03 ,X, Y PF 6 , BF 4 , B [C 6 H 5 _ 4 , B [C 6 F 5 ], B [C 6 H 3 (mCF 3 ) 2 ] 4 , C10, S0 4 , CF 3 S0 3 or FS0 3 ,
L^L^L^L^L5 Phosphan, Arsan, Stiban, Carbenoid mit Hete- rosubstitution, Amin, Nitril oder Kohlenmon- oxid,L ^ L ^ L ^ L ^ L 5 phosphine, arsan, stiban, carbenoid with hetero substitution, amine, nitrile or carbon monoxide,
n,m unabhängig voneinander 0 oder 1 bedeuten .n, m independently of one another 0 or 1 mean.
3. Dikationische Rutheniumkomplexe der allgemeinen Formel I nach Anspruch 1, dadurch gekennzeichnet, daß • 3. Dicationic ruthenium complexes of the general formula I according to claim 1, characterized in that •
R^R^R^R4 Wasserstoff oder Phenyl,R ^ R ^ R ^ R 4 is hydrogen or phenyl,
X,Y BF oder B [C6H3 (mCF3) 2] 4,X, Y BF or B [C 6 H 3 (mCF 3 ) 2 ] 4 ,
L^L2 P (Cyclohexyl) 3 oder P (iso-Propyl) 3,L ^ L 2 P (cyclohexyl) 3 or P (isopropyl) 3 ,
L3,L4 CH3CN,L 3 , L 4 CH 3 CN,
m 0 undm 0 and
nn
bedeuten.mean.
4. Verfahren zur Herstellung der Rutheniumkomplexe nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man kationische Vinyl-Komplexe der allgemeinen Formel4. A process for the preparation of the ruthenium complexes according to any one of claims 1 to 3, characterized in that cationic vinyl complexes of the general formula
[Ru(R1C=CR2R3)L1L2L3L]X mit Säuren HY oder Alkylierungsmitteln R4Y bei Temperaturen von (-100) bis +200°C und einem Druck von 0,1 bis 20 bar umsetzt.[Ru (R 1 C = CR 2 R 3 ) L 1 L 2 L 3 L] X with acids HY or alkylating agents R 4 Y at temperatures from (-100) to + 200 ° C and a pressure of 0.1 to 20 implemented in cash.
5. Verfahren zur Herstellung der Rutheniumkomplexe nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man kationische Carben-Komplexe der allgemeinen Formel [RuZ(=CR1CR2R3R)L1L2L3L]X oder kationische Carbin-Komplexe der allgemeinen Formel [RuRxZ (≡CCR2R3R4) L1L2L3L4] X, in der Z ein eifach negativ geladener koordinierender Ligand ist, mit Salzen MY bei Temperaturen von (-100) bis +200°C und einem Druck von 0,1 bis 20 bar umsetzt.5. A process for the preparation of the ruthenium complexes according to one of claims 1 to 3, characterized in that cationic carbene complexes of the general formula [RuZ (= CR 1 CR 2 R 3 R) L 1 L 2 L 3 L] X or cationic Carbine complexes of the general formula [RuR x Z (≡CCR 2 R 3 R 4 ) L 1 L 2 L 3 L 4 ] X, in which Z is a negatively charged coordinating ligand, with salts MY at temperatures of (-100 ) up to + 200 ° C and a pressure of 0.1 to 20 bar.
6. Verfahren zur Herstellung der Rutheniumkomplexe nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man Komplexe der Zusammensetzung [RuX1X2L1L2L3L4] mit Vinyl-Grignard- Reagenzien R3R2C=CR1MgX oder anderen Vinyl-Metall-Reagenzien bei Temperaturen von (-100) bis +100°C und einem Druck von6. Process for the preparation of the ruthenium complexes according to one of claims 1 to 3, characterized in that complexes of the composition [RuX 1 X 2 L 1 L 2 L 3 L 4 ] with vinyl Grignard reagents R 3 R 2 C = CR 1 MgX or other vinyl metal reagents at temperatures from (-100) to + 100 ° C and a pressure of
0,5 bis 5 bar umsetzt und anschließend mit Salzen MY, Säuren HY oder Alkylierungsmitteln R4Y bei Temperaturen von 0 bis 100°C und einem Druck von 0,5 bis 5 bar umsetzt.0.5 to 5 bar and then reacted with salts MY, acids HY or alkylating agents R 4 Y at temperatures from 0 to 100 ° C. and a pressure of 0.5 to 5 bar.
7. Verwendung der Rutheniumkomplexe nach einem der Ansprüche 1 bis 3 zu Metathesereaktionen von Olefinen. Verwendung der Rutheniumkomplexe nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß diese Rutheniumkomplexe ohne Aktivierung oder in situ mit Säuren HY aktiviert eingesetzt werden. 7. Use of the ruthenium complexes according to one of claims 1 to 3 for metathesis reactions of olefins. Use of the ruthenium complexes according to one of Claims 1 to 3, characterized in that these ruthenium complexes are used without activation or activated in situ with acids HY.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109225334A (en) * 2018-07-20 2019-01-18 吉林化工学院 A kind of ruthenium olefin metathesis catalyst and its preparation method and application with ortho position steric hindrance structure

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999000396A1 (en) * 1997-06-25 1999-01-07 Ciba Specialty Chemicals Holding Inc. Ruthenium and osmium carbene catalysts
WO1999026949A1 (en) * 1997-11-21 1999-06-03 California Institute Of Technology Schiff base derivatives of ruthenium and osmium olefin metathesis catalysts
DE19800934A1 (en) * 1997-08-22 1999-07-15 Basf Ag Ruthenium complexes suitable as metathesis catalysts
WO1999058538A1 (en) * 1998-05-08 1999-11-18 Basf Aktiengesellschaft Cationic ruthenium complexes, their production and their use
EP1024144A2 (en) * 1999-01-29 2000-08-02 Zeon Chemicals L.P. Ruthenium catalysts for metathesis reactions of olefins

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999000396A1 (en) * 1997-06-25 1999-01-07 Ciba Specialty Chemicals Holding Inc. Ruthenium and osmium carbene catalysts
DE19800934A1 (en) * 1997-08-22 1999-07-15 Basf Ag Ruthenium complexes suitable as metathesis catalysts
WO1999026949A1 (en) * 1997-11-21 1999-06-03 California Institute Of Technology Schiff base derivatives of ruthenium and osmium olefin metathesis catalysts
WO1999058538A1 (en) * 1998-05-08 1999-11-18 Basf Aktiengesellschaft Cationic ruthenium complexes, their production and their use
EP1024144A2 (en) * 1999-01-29 2000-08-02 Zeon Chemicals L.P. Ruthenium catalysts for metathesis reactions of olefins

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
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 (en) * 2018-07-20 2019-01-18 吉林化工学院 A kind of ruthenium olefin metathesis catalyst and its preparation method and application with ortho position steric hindrance structure
CN109225334B (en) * 2018-07-20 2021-05-18 吉林化工学院 Ruthenium olefin metathesis catalyst with ortho-position steric hindrance structure and preparation method and application thereof

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