EP1311520A1 - Complexes de ruthenium contenant des carbenoides - Google Patents

Complexes de ruthenium contenant des carbenoides

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Publication number
EP1311520A1
EP1311520A1 EP01967261A EP01967261A EP1311520A1 EP 1311520 A1 EP1311520 A1 EP 1311520A1 EP 01967261 A EP01967261 A EP 01967261A EP 01967261 A EP01967261 A EP 01967261A EP 1311520 A1 EP1311520 A1 EP 1311520A1
Authority
EP
European Patent Office
Prior art keywords
ligands
ruthenium complexes
complexes
independently
rucl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01967261A
Other languages
German (de)
English (en)
Inventor
Wolfram Stueer
Jörn KARL
Michael Röper
Stefan Jung
Justin Wolf
Helmut Werner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1311520A1 publication Critical patent/EP1311520A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
    • 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

Definitions

  • the invention relates to ruthenium complexes containing carbenoids, which can be used, for example, as catalysts in metathesis reactions, and to processes for their preparation.
  • C C double bonds.
  • a distinction is made, for example, between self-metathesis, in which an olefin merges into a mixture of two olefins of different molar mass (example: propene ⁇ ethene + 2-butene), and cross- or co-metathesis, which is a reaction of two different ones Olefins describes (propene + 1-butene ⁇ ethene + 2-pentene).
  • olefin metathesis is syntheses of unsaturated polymers by ring-opening metathesis polymerization (ROMP) of cyclic olefins and acyclic diene metathesis polymerization (ADMET) of ⁇ , ⁇ -dienes. More recent applications relate to the selective ring opening of cyclic olefins with acyclic olefins and ring closure reactions (RCM), with which - preferably from oc, ⁇ -dienes - unsaturated rings of different ring sizes can be produced.
  • RCM ring closure reactions
  • homogeneous and heterogeneous transition metal compounds are suitable as catalysts for metathesis reactions, in particular those of VI. - VIII.- Subgroup of the Periodic Table of the Elements as well as homogeneous and heterogeneous catalyst systems in which these compounds are contained.
  • these catalysts can in some cases be deactivated quickly.
  • the activity of the catalysts and the rate of deactivation are very dependent on the olefin.
  • the degree of substitution of the double bond as well as the position of functional groups for the double bond play a significant role.
  • heteroatom-substituted carbenes have been used as ligands instead of the phosphine ligands. In free form, these have an electron sextet on a carbon atom.
  • N-heterocyclic carbenes as complex ligands whose ring is derived from imidazole or triazole.
  • the task was to develop basic ligand structures that allow a varied variation of the substituents and the framework to enable a variable catalyst design. It should be possible to vary the steric conditions and the electronic conditions in many ways. The aim was to find generally applicable syntheses that can be transferred to a variety of starting materials and thus allow the synthesis of a large number of ligands. Furthermore, the necessary starting materials should be as commercially available or easy to manufacture as possible. In order to achieve a high throughput, the synthesis should be transferable to an automatic machine in order to enable the automated construction of a ligand library and thus a catalyst library. This should make it possible to optimize ruthenium metathesis catalysts specifically for a substrate.
  • L ⁇ L 2 independently of one another, neutral electron donor ligands which are coordinated as carbenoids to the metal center and can be connected via a bridge W having 0 to 20 carbon atoms which can be part of a cyclic or aromatic group and can be interrupted by heteroatoms, with the exception of C, N-heterocyclic five-membered systems,
  • the neutral electron donor ligands L and L independently of one another have the general formula C, RR
  • R 1 to R 4 independently of one another, denote electron pairs, hydrogen or, optionally substituted, C 1-20 alkyl, C 6-2 o aryl or C 20 alkylaryl radicals, where (R 1 and R 2 ) and / or ( R 2 and R 3 ) and / or (R 3 and R 4 ) can together form a cyclic radical, and
  • E 1 and E 2 independently of one another elements of the group B, CR 5 , SiR 5 with R 5 as defined for R 1 to R 4 , represent N, P, As, Sb, O, S according to their valency.
  • the neutral electron donor ligands L 1 and L 2 are particularly preferably selected independently of one another from cyclic and non-cyclic diaminocarbenes (I, II with n ⁇ 1, III), aminooxycarbenes (IV), bisoxycarbenes, aminothiocarbenes (V), ammophosphinocarbenes, phosphinooxycarbenes ( VII), PhospMnophosphinocarbenen (VIII), Phosphinosilylcarbenen (IX) and
  • the anionic ligands are preferably weak or non-coordinating anions, for example ClO “ , PF 6 “ , BF 4 “ , BAr 4 " or sulfonate.
  • the electronic properties of the carbene carbon atom can be determined by the
  • variable substitution with the same or different fragments ER R or E 2 R 3 R 4 can be largely controlled.
  • the electron deficiency in diamino carbenes is reduced by the ⁇ donor, ⁇ acceptor character of the NR 2 fragments.
  • diboryl carbenes on the other hand, the electron deficiency of the carbon atom is exacerbated by the boron atoms acting as ⁇ acceptors and ⁇ donors.
  • the phosphoniosilyl carbenes are located (see Chem. Rev. 2000, 100, 39-91).
  • the properties of the catalyst can thus be varied by coordinating with the transition metal ruthenium.
  • Another object of the invention is the use of these catalyst systems in metathesis reactions of olefins.
  • the above-mentioned compounds are characterized by a significantly expanded variability of the structures and by a simple preparation of the property-determining ones Ligands L, L.
  • the complexes of type A or B can either react with the olefin without activation, or be activated in situ with acids HX or with light, where X is, for example, CF CO 2 " or CF 3 SO 3 " .
  • the ligands used in the catalysts according to the invention can be produced on a large scale with different structures with the aid of automatic synthesizers. This makes it possible to automatically produce large ligand and catalyst libraries.
  • the ligands and catalysts according to the invention allow extensive variation in steric and electronic terms. This makes it possible to manufacture a large number of catalysts with different properties, which are then suitable for one can be subjected to catalyst screening and "tuning" for a specific implementation.
  • an intended implementation can be carried out in parallel in a large number of reactors using different catalysts from the catalyst library, the catalyst or catalysts identified as being the most active or selective Corresponding combinatorial or automated production processes using automatic machines for this purpose are known, see for example AM La Pointe, J. Comb. Chem. 1999, 1, 101-104.
  • the ruthenium complexes according to the invention can be prepared by any suitable method, such as those listed in the documents cited above.
  • the invention thus relates to a process for the preparation of the ruthenium complexes according to the invention by reacting ruthenium complexes of the general formula [RuHX (H 2 ) LL] with the free ligands L and L and acids HX 2 or salts thereof, and alkynes or R "-C 6 H 5 , where L, L are neutral two-electron donors.
  • the invention relates to a process for the preparation of the ruthenium complexes by reaction of RuCl 3 • xH 2 O or [RuCl 2 (olefin)] 2 or [RuCl 2 (COD)] n with the free ligands L 1 and L 2, or with the salts [HL ⁇ X 1 and [HL 2 ] X 2 in the presence of a base and hydrogen to form precursor compounds which in turn are reacted with alkynes and acids HX 1 and HX 2 .
  • the invention also relates to a process for the preparation of ruthenium complexes B by the reaction of [RuCl 2 (arene)] 2 or [(arene) RuCl 2 (L * )] 2 with the free ligand L 1 or the salt [HL ⁇ X 1 in the presence of a base, where L is a neutral two-electron donor.
  • these processes can be carried out automatically in parallel in a plurality of reaction vessels.
  • the synthesis of the active components A and / or B can be carried out starting from numerous organometallic starting materials, for example
  • Arenameric complexes such as [(p-cymene) RuCl 2 (PPh 3 )] are obtained by stirring the dimeric starting materials with PPh 3 .
  • [(p-cymene) RuCl 2 ] reacts with PPh 3 in organic solvents to [(p-cymene) RuCl 2 (PPh 3 )].
  • the latter compound or a dimer such as [(p-cymene) RuCl 2 ] 2 is reacted with the free carbene ligands of type C to give the active components B according to the invention, with one equivalent of PPh 3 being split off.
  • the carbenes of type C can be produced in the presence of the organometallic starting material by reacting the carbene precursors [L ⁇ JY or P ⁇ H ⁇ Y " with strong bases, such as, for example, KOtBu, LDA (lithium diisopropylamide) and react directly to the active components A and / or B without being isolated beforehand.
  • strong bases such as, for example, KOtBu, LDA (lithium diisopropylamide)
  • Reactions to the active components A and / or B are carried out in organic solvents under an inert gas atmosphere.
  • the reaction is preferably carried out in THF or toluene or mixtures of the two at temperatures from -100 to + 100 ° C., preferably 0 to 100 ° C. and pressures from 1 mbar to 100 bar, preferably at 0.5 to 5 bar.
  • the reaction can be carried out using one or more molar equivalents of C or precursors of C.
  • the compositions obtained in this way and containing the active components A and / or B can be used in situ as a highly active metathesis catalyst system or isolated and stored under an inert gas atmosphere. If necessary, the active components A or B are used in isolated form.
  • the reaction of substances of general structure C or their precursors with suitable ruthenium complexes to form A or B is complete after 1 s to 10 h, preferably after 3 s to 1 h.
  • Suitable reaction vessels are generally glass or steel containers, which may be lined with ceramic.
  • Another object of the invention is the use of these catalyst systems in metathesis reactions of olefins.
  • the abovementioned compounds are distinguished by a significantly expanded variability of the structures and by a simple preparation of the property-determining ligands L, L.
  • the catalysts can therefore be easily optimized for a specific substrate.
  • the catalyst complexes A and B thus obtained can be used, inter alia, for
  • ADMET Acyclic diene metathesis polymerization
  • RCM Ring closure metathesis

Landscapes

  • 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

Dans les complexes de ruthénium de la formule générale (A) ou (B), X<1> et X<2> représentent indépendamment des ligands anioniques à une ou plusieurs dents ; R, R', et R'' représentent indépendamment de l'hydrogène ou des restes C1-20-alkyl, C6-20-aryl, ou C7-20-alkylaryl éventuellement substitués ; et, L<1> et L<2> représentent indépendamment des ligands neutres de donneurs d'électrons, coordonnés sur le centre métallique en tant que carbénoïdes, et pouvant être liés par un pont W portant de 0 à 20 atomes de carbone, ledit pont étant un constituant d'un groupe cyclique ou aromatique et pouvant être interrompu par des hétéroatomes, avec exception de systèmes pentacycliques C, N hétérocycliques.
EP01967261A 2000-08-11 2001-08-10 Complexes de ruthenium contenant des carbenoides Withdrawn EP1311520A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10039389A DE10039389A1 (de) 2000-08-11 2000-08-11 Carbenoide enthaltende Rutheniumkomplexe
DE10039389 2000-08-11
PCT/EP2001/009295 WO2002014336A1 (fr) 2000-08-11 2001-08-10 Complexes de ruthenium contenant des carbenoides

Publications (1)

Publication Number Publication Date
EP1311520A1 true EP1311520A1 (fr) 2003-05-21

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP01967261A Withdrawn EP1311520A1 (fr) 2000-08-11 2001-08-10 Complexes de ruthenium contenant des carbenoides

Country Status (11)

Country Link
US (1) US20030195357A1 (fr)
EP (1) EP1311520A1 (fr)
JP (1) JP2004506644A (fr)
KR (1) KR20030022888A (fr)
CN (1) CN1447815A (fr)
AU (1) AU2001287677A1 (fr)
CA (1) CA2419368A1 (fr)
DE (1) DE10039389A1 (fr)
EA (1) EA200300260A1 (fr)
MX (1) MXPA03001161A (fr)
WO (1) WO2002014336A1 (fr)

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Publication number Priority date Publication date Assignee Title
TWI295410B (en) * 2002-11-29 2008-04-01 Zeon Corp Radiation-sensitive resin composition
US7094898B2 (en) * 2003-05-29 2006-08-22 University Of Ottawa Ruthenium compounds, their production and use
CN100569662C (zh) * 2007-12-12 2009-12-16 中国科学院长春应用化学研究所 有机配体包覆的氧化钌纳米粒子的制备方法
US8759541B2 (en) * 2008-07-08 2014-06-24 Avinash N. Thadani Chiral acyclic diaminocarbene ligands, precursors therefore and their use in organic synthesis reactions
GB0822064D0 (en) * 2008-12-03 2009-01-07 Johnson Matthey Plc Process for preparing cationic ruthenium complexes
WO2011059803A2 (fr) * 2009-10-29 2011-05-19 Board Of Regents, The University Of Texas System Ruthénium-alkylidènes contenant des diaminocarbènes acycliques pour obtenir de faibles rapports e/z dans une métathèse croisée

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Publication number Priority date Publication date Assignee Title
US5160926A (en) * 1989-06-28 1992-11-03 Schweitzer Engineering Laboratories, Inc. Display transducer apparatus
US6011480A (en) * 1997-07-23 2000-01-04 Schweitzer Engineering Laboratories, Inc. Protection quality capability for protective relays used in an electric power system
DE19902439A1 (de) * 1999-01-22 2000-08-03 Aventis Res & Tech Gmbh & Co Homo- und heterobimetallische Alkylidenkomplexe des Rutheniums mit N-heterocyclischen Carbenliganden und deren Anwendung als hochaktive, selektive Katalysatoren für die Olefin-Metathese

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0214336A1 *

Also Published As

Publication number Publication date
WO2002014336A1 (fr) 2002-02-21
CN1447815A (zh) 2003-10-08
JP2004506644A (ja) 2004-03-04
DE10039389A1 (de) 2002-02-21
MXPA03001161A (es) 2003-10-14
EA200300260A1 (ru) 2003-08-28
CA2419368A1 (fr) 2003-02-10
AU2001287677A1 (en) 2002-02-25
US20030195357A1 (en) 2003-10-16
KR20030022888A (ko) 2003-03-17

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