WO2010013239A2 - Synthèse de complexes de métaux de transition stables à c-(sp<sp>3</sp>)-carbo-métallation - Google Patents

Synthèse de complexes de métaux de transition stables à c-(sp<sp>3</sp>)-carbo-métallation Download PDF

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Publication number
WO2010013239A2
WO2010013239A2 PCT/IL2009/000736 IL2009000736W WO2010013239A2 WO 2010013239 A2 WO2010013239 A2 WO 2010013239A2 IL 2009000736 W IL2009000736 W IL 2009000736W WO 2010013239 A2 WO2010013239 A2 WO 2010013239A2
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Prior art keywords
transition metal
metal complex
dienophile
conjugated diene
complexes
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PCT/IL2009/000736
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English (en)
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WO2010013239A3 (fr
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Dmitri Gelman
Clarite Azerraf
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Yissum Research Development Company Of The Hebrew University Of Jerusalem, Ltd
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Publication of WO2010013239A2 publication Critical patent/WO2010013239A2/fr
Publication of WO2010013239A3 publication Critical patent/WO2010013239A3/fr

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    • 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
    • C07F15/006—Palladium compounds
    • 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
    • C07F15/0086—Platinum compounds
    • 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
    • C07F15/04—Nickel compounds

Definitions

  • Transition metal catalysts are used for a variety of organic processes and have an immense importance in some industrial fields, such as in the reduction of ketones to alcohols, or of imines to amines and in the hydrogenation of olefins to alkanes.
  • enantiomerically enriched products can be prepared by asymmetric transfer hydrogenation when the transition metal catalyst comprises an enantiomerically enriched ligand (also defined as “optically active” or “chiral non racemic” ligand) , ensuring that the double bond of a prochiral compound is asymmetrically reduced.
  • this asymmetric transfer hydrogenation is often employed for the preparation of enantiomerically enriched alcohols from prochiral ketones.
  • organometallic cyclometalated complexes of second- and third-row transition metals have necessitated synthetic methods for preparing them efficiently.
  • One synthetic route is reacting lithiated ligands with platinum or palladium compounds having good leaving groups (see for example, WO 00/57676) .
  • Organometallic cyclometalated complexes may also be formed by a direct reaction on the cyclometalating ligand, wherein the carbon-hydrogen is activated and replaced by the carbon-metal bond (see, for example US Patent No. 7,423,151).
  • Pincer ligands are ligands which bind to the metal through at least three coplanar sites: two donor atoms and a metalated carbon which is linked to the metal in a ⁇ (sigma) metal-carbon bond.
  • complexes having general formula I were prepared by attaching a bulky, bidentate ligand through a third center on an sp 3 cyclometalated carbon, thereby forming a tridentate pincer-type ligand having an sp 3 cyclometalated carbon attached to the metal center.
  • M is selected from Ir or Rh
  • Z is selected from:
  • Z 1 R 1 is independently selected from: Ci-C ⁇ -alkyl, aryl, alkoxy, aryloxy, Ci-C 6 -alkylamine, arylamine, halogen, N, 0 or hydrogen;
  • R 3 and R 4 are independently selected from: Ci-C ⁇ - alkyl, aryl, alkoxy, aryloxy, Ci-Cg-alkylamine and arylamine;
  • Wi and W 2 are independently selected from P, As, N and 0;
  • X 1 and X 2 are independently selected from: halogen, H, Ci-C 6 -alkyl or null;
  • Y is selected from CO, RCN, N 2 , alkene or null;
  • R is selected from: Ci-C 6 ⁇ alkyl, aryl, alkoxy, aryloxy, Ci-C 6 -alkylamine and arylamine.
  • the method described in PCT/IL2009/00356 involved mixing a precursor complex of the formula MXL 2 and/or hydrates thereof (wherein X is a halogen and L is a monodentate ligand, or wherein L 2 is a bidentate ligand) with a ligand having the structure of Formula III in a solvent, thereby obtaining a reaction mixture.
  • M, R 1 , R 2 , R 3 , R 4 , Z, W ⁇ and W 2 are as defined for formula I hereinabove .
  • reaction mixture was then heated to form the complex of formula I within the reaction mixture. Subsequently, the product was isolated from the reaction mixture .
  • the Diels-Alder reaction otherwise known as a cycloaddition reaction, involves reacting a conjugated diene with a double or triple bond, called a dienophile.
  • the reaction is stereospecific, and is one of the few reactions that can be used to form two new bonds at the same time.
  • the present invention provides a novel synthetic path for the preparation of a family of organometallic complexes recently described in PCT/IL2009/000356.
  • This family of complexes presents a new class of electron-rich C (sp 3 ) -cyclometalated complexes of transition metals (e.g. rhodium, iridium, platinum, palladium, nickel, ruthenium, etc.) based on the dibenzobarrelene and dibenzobarrelene- like scaffolds.
  • transition metals e.g. rhodium, iridium, platinum, palladium, nickel, ruthenium, etc.
  • the rigidity and chemical inertness of the polycyclic backbone in combination with the absence of easily abstractable ⁇ -hydrogens results in the formation of thermally and conformationally stable compounds, that are nonetheless extremely active catalysts for a variety of processes, such as polymerization, hydrogenation and more.
  • the inventors have now developed and demonstrated a general synthetic route toward preparing carbometalated transition metal complexes by a Diels-Alder cycloaddition reaction, having shown that a transition metal complex can act as a conjugated diene and react with a dienophile to successfully produce the cycloaddition reaction product.
  • a process for preparing a carbometalated transition metal complex by reacting a transition metal complex having at least one conjugated diene ligand, with a dienophile, in a Diels-Alder cycloaddition reaction.
  • transition metal complex refers to a transition metal complex containing a metal- carbon bond.
  • transition metal complex will be understood by one skilled in the art as a compound which contains a transition metal linked to one or more ligands .
  • the process of the invention is suitable for the preparation of complexes of a variety of transition metals, in particular with any metal from Group VIII of the Periodic Table of Elements.
  • transition metals include silver (Ag) , palladium (Pd) , platinum (Pt) , ruthenium (Ru) , rhodium (Rh) , iridium (Ir) , copper (Cu) , nickel (Ni) , cobalt (Co) , osmium (Os) , and combinations thereof.
  • ligand otherwise known as “complexing agent” or “chelating agent”, as used herein, refers to atoms or groups of atoms, which form coordination bonds to the central transition metal atom.
  • the ligands can have different ligations, such as to be monodentate, bidentate, tridentate, tetradentate etc.
  • conjugated diene ligand refers to a ligand that includes at least two conjugated double bonds, each of which can be any type of double bond.
  • the conjugated diene ligand may be a cyclic conjugated diene ligand, in which case it refers to a conjugated diene ligand having at least one ring that includes at least one conjugated double bond located therein.
  • the one or more other conjugated double bonds for example, may also be located on the ring and/or may be located in a group attached to the ring.
  • the transition metal complex having at least one conjugated diene ligand is an anthracene-based 9-C (sp 2 ) -metalated complex.
  • Such complexes are structurally simple to prepare, for example by heating a solution of the anthracene-based diphosphine ligand with an appropriate transition metal precursor, such as PdCl 2 , PtCl 2 , NiCl2 etc., with or without a base (e.g. EtsN) (for more details see: (a) M. W. Haenel et al., Chem. Ber., 1991, 124, 333; (b) M. W. Haenel et al . , Angew.
  • dienophile describes a compound which can interact with a conjugated diene in a Diels-Alder cycloaddition reaction. Dienophiles are typically unsaturated compounds, having a double bond or a triple bond. Examples of dienophiles include alkenes, alkynes, diazenes or carbazenes.
  • the dienophile is selected from:
  • Ra, Rb, Rc and Rd are independently selected from: Ci-C ⁇ -alkyl, aryl, alkoxy, aryloxy, C 1 -Cg- alkylamine, arylamine, halogen, N, 0 or hydrogen.
  • Diels-Alder reactions are facilitated by a combination of electron-withdrawing substituents on one of the reactants (diene or dienophile) and electron- releasing substituents on the other.
  • the reaction between the conjugated diene and the dienophile is also termed "4+2 Diels-Alder cycloaddition", referring to the ' electrocyclic reaction that involves the 4 ⁇ -electrons of the diene and the 2 IT- electrons of the dienophile.
  • C (sp 3 ) -cyclometalated compounds via one-step transformation of their C(sp 2 ) precursors, for example by effecting a 4+2 Diels-Alder cycloaddition of an anthracene-based 9-C (sp 2 ) -metalated complexes as the conjugated diene with a suitable dienophile.
  • the carbometalated transition metal complexes which are to be prepared by this process are C (sp 3 ) -carbometalated transition metal complexes containing at least one pincer ligand which is linked to the transition metal center through a carbon, termed Ca, and through two donor atoms W 1 and W 2 .
  • Pincer ligands combine bulkiness and steric hindrance with controllable electronic effects, and are also characterized in that the atoms Wi, W 2 and Ca are coplanar .
  • These complexes are further characterized in that the carbon atom linked to the metal (Ca) has to be part of a ring system (s), making Ca a cyclometalated carbon.
  • the Ca carbon has to be in an sp 3 hybridization, and finally, the Ca carbon has to be bonded to three C ⁇ carbons and each of these C ⁇ carbons has to be linked only to non-hydrogen atoms. Namely, there should be no hydrogens linked to either Ca or to any carbon atom adjacent to Ca. Hence, no a-hydrogens or ⁇ -hydrogens, relative to the metal center, are present.
  • M is a transition metal selected from nickel (Ni) , palladium (Pd) , platinum (Pt) , ruthenium (Ru) , iridium (Ir) or rhodium (Rh) .
  • the metal is directly bound to an sp 3 hybridized cyclic carbon which is part of a pincer ligand.
  • the direct metal-carbon bond renders this carbon an ⁇ -carbon relative to the metal center. It should be noted that neither this ⁇ -carbon, nor the carbons adjacent to it ( ⁇ -carbons) have any hydrogens thereon.
  • the pincer complex of formula A belongs to a special class of pincer complexes, which, as described in detail in PCT/IL2009/00356, are characterized by a useful combination of stability and reactivity in catalytic hydrogenation reactions .
  • X 1 and X 2 are independently selected from: halogen, hydrogen, Ci-Cg-alkyl, or null; When either X 1 or X 2 is a halogen, it can be fluorine, chlorine, bromine, iodine or combination thereof, but is preferably one of the first three mentioned, more preferably chlorine.
  • Y is selected from CO, RCN, N 2 , alkene or null. It should be noted that converting any of these groups to another can be done according to known chemical procedures, and therefore complexes containing any of these Y groups are interchangeable with one another.
  • R is selected from: Ci-C ⁇ -alkyl, aryl, alkoxy, aryloxy, Ci-C ⁇ -alkylamine and arylamine.
  • the aryl is phenyl.
  • Wi and W 2 are donor atoms, independently selected from phosphorus (P) , arsenic (As) , nitrogen (N) or oxygen (O) .
  • P phosphorus
  • As arsenic
  • N nitrogen
  • O oxygen
  • at least one donor atom is a phosphorus (P) atom. More preferably, both donor atoms are phosphorus (P) atoms.
  • R 3 and R 4 are independently selected from: Ci-C ⁇ - alkyl, aryl, alkoxy, aryloxy, Ci-C ⁇ -alkylamine and arylamine; Preferably, R 3 and R 4 are independently selected from Ci-C ⁇ -alkyl or aryl groups. More preferably, the aryl is phenyl.
  • R 3 and R 4 cannot be hydrogen, there are no ⁇ -hydrogens (relative to the metal center) on the donor atoms W.
  • R 3 and R 4 are chosen such that there will be also no ⁇ -hydrogens on the substituents .
  • R 1 and R 2 represent one or more substituent on the rings, whereas these substituents are independently selected from: Ci-C ⁇ -alkyl, aryl, alkoxy, aryloxy, Ci-C ⁇ - alkylamine, arylamine, halogen, N, O or hydrogen;
  • Z is selected from aryl, Ci-C ⁇ -alkyl or alkenyl groups.
  • Z is selected from one of groups Z 1 - Z 4 , as depicted below:
  • Ra, Rb, Rc and Rd are independently selected from: Ci-C 6 -alkyl, aryl, alkoxy, aryloxy, Ci-C 6 -alkylamine, arylamine, halogen, N, 0 or hydrogen;
  • the process to obtain the complexes of general formula A comprises reacting a conjugated diene transition metal complex having general formula B
  • R 1 , R 2 , R 3 , R 4 , W 1 , W 2 , X 1 , X 2 , Y, Ra, Rb, Rc and Rd are as defined hereinabove.
  • the complexes of general formula B having the conjugated diene ligands, are anthracene-based 9-C (sp 2 )- metalated complexes and are readily available and structurally simple to prepare or obtain, as described hereinabove.
  • the dienophiles H x -H 4 represent several groups of alkenes (H 3 and H 4 ) and alkynes (H 1 and H 2 ) . It should be noted that the alkyne groups, in particular the strained triple bond of the benzyne (H 1 ) make very good dienophile.
  • the reaction of complexes of general formula B with the dienophiles H 1 -!! 4 will result in cycloaddition products of general formula A containing Z 3- -Z 4 groups, respectively.
  • the conjugated diene transition metal complex is a complex of formula Bl:
  • M is a transition metal selected from nickel (Ni) , palladium (Pd) and platinum (Pt) , and the dienophile is dimethyl acetylenedicarboxylate (DMAD) , which is of the H 2 type:
  • the process described herein is conducted such that the conjugated diene is first reacted with a solvent, to produce a suspension or a solution, prior to reacting it with the dienophile under heating.
  • Any solvent may be used for this stage; however, polar solvents are preferable, due to a better solubility of the starting materials and products.
  • polar solvent refers to a solvent that has a permanent electrical dipole moment or a solvent that is capable of dissolving polar substances.
  • Some preferable solvents for the purpose of the present invention include, but are not limited to, methoxybenzene (anisole) , diethylene glycol dimethyl ether (diglyme) and dimethyl ether (DME) .
  • the process described herein is conducted under reflux, generally at a temperature ranging from about 70 0 C to about 300 0 C. Typical reaction times may be from about 7 hours to about 50 hours. Preferably the reflux is conducted for about 24 hours .
  • the method described herein may optionally further comprise separating the product from the reaction mixture and purifying the complex to obtain a purified form thereof.
  • the isolation and purification of the product can be conducted in any number of commonly used techniques, such as concentration of the reaction mixture by partially evaporating the solvent, precipitation of the complex by the addition of an anti-solvent, filtration of the solid
  • 1, 8-dibromoanthracene was synthesized according to 0. Grossman et al., Organometallics 2006, 25, 375.
  • NiCl 2 (DME) and PtCl 2 (CH 3 CN) 2 were obtained from Strem. All other chemicals and metal precursors were purchased from Sigma-Aldrich and were used without further purifications .
  • IR was measured using a Perkin Elmer 16PC FTIR.
  • Gas chromatography analyses were performed on a Hewlett Packard 5890 instrument with a FID detector and a Hewlett Packard 25 m x 0.2 mm i.d. Supelcowax-10 capillary column .
  • Thermal stability of the complexes was determined using Thermogravimetric analysis (TSA) on a Perkin Elmer Pyris 1 TGA.
  • TSA Thermogravimetric analysis
  • X-ray crystallographic analysis was performed on a Bruker APEX CCD X-ray system.
  • Yields refer to isolated yields of compounds having purity greater than 95% as determined by proton Nuclear Magnetic Resonance spectroscopy (IH-NMR) analysis .
  • IH-NMR proton Nuclear Magnetic Resonance spectroscopy
  • a suspension was prepared by mixing compound 1 (500 mg, 0.73 mmol and PdCl 2 (CH 3 CN) 2 (189.1 mg, 0.73 mmol) in ethylene glycol monomethyl ether (20 ml) . This suspension was heated at reflux to about 200 0 C for 2 hours. After cooling to room temperature, the green precipitate was filtered off, washed twice with methanol and dried in high vacuum to yield compound 3 (442 mg, 88% yield) . 1 H
  • a suspension was prepared by mixing compound 1 (500 mg, 0.73 mmol and NiCl 2 (DME) (160.4 mg, 0.73 ramol) in ethylene glycol monomethyl ether (20 ml) .
  • diisopropylethylamine (0.12 ml, 0.73 mmol) was added and the mixture was heated at reflux to about 200 0 C for 2 hours. After cooling to room temperature the yellow precipitate was filtered off, washed twice with methanol and dried in high vacuum to yield Compound 4
  • a suspension was prepared by mixing compound 1 (500 mg, 0.73 mmol) and PtCl 2 (CH 3 CN) 2 (254 mg, 0.73 mmol) in ethylene glycol monomethyl ether (20 ml) .
  • diisopropylethylamine (0.12 ml, 0.73mmol) was added and the mixture was heated at reflux to about 200 0C for 2 hours. After cooling to room temperature the green precipitate was filtered off, washed twice with methanol and dried in high vacuum to yield Compound 5
  • a suspension was prepared by mixing Compound 4 (200 mg, 0.31 mmol) in diethylene glycol dimethyl ether
  • a suspension was prepared by mixing Compound 5 (200 mg, 0.26 mmol) in diethylene glycol dimethyl ether (diglyme, 5 ml) .
  • DMAD dimethyl acetylenedicarboxylate
  • the obtained mixture was heated at reflux to about 100 0 C for 24 hours.
  • the solvent was reduced by evaporation under reduced pressure.
  • An addition of methanol (5 cc) to the mixture results in a light grey precipitate.
  • the solid was filtered off, washed twice with methanol and dried in high vacuum to yield Complex 8 (167 mg, 80% yield) .

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

Abstract

La présente invention concerne un nouveau procédé permettant de préparer des complexes de métaux de transition à carbo-métallation, en faisant réagir un complexe de métal de transition possédant au moins un ligand diène conjugué avec un diénophile, au cours d'une réaction de cycloaddition Diels-Alder. Dans un mode de réalisation spécifique, l'invention concerne la transformation de complexes à base d'anthracène ayant subi une 9-C(sp2)-métallation en complexes à C(sp3)-métallation, par synthèse organique impliquant la réaction Diels-Alder.
PCT/IL2009/000736 2008-07-31 2009-07-29 Synthèse de complexes de métaux de transition stables à c-(sp<sp>3</sp>)-carbo-métallation WO2010013239A2 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130094217A (ko) * 2010-06-11 2013-08-23 유니버셜 디스플레이 코포레이션 지연 형광 ｏｌｅｄ

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
AZERRAF, C. ET AL.: "Diels-Alder cycloaddition as a new approach towards stable PC(sp3)P-metallated compounds" CHEMICAL COMMUNICATIONS, no. 4, 2009, XP002555054 *
MASUDA, K. ET AL.: "mechanistic study on ruthenium Cp- and CP*Ru+-mediated cycloaddition between conjugated dienes and acetylenes" ORGANOMETALLICS, vol. 12, no. 6, 1993, pages 2221-2226, XP002555052 *
O'CONNOR, J.M. ET AL.: "iridacyclopentadiene reactions with terminal alkynes:tandem cycloaromitization and orthometallation" ORGANOMETALLICS, vol. 20, no. 17, 2003, pages 3710-3717, XP002555053 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130094217A (ko) * 2010-06-11 2013-08-23 유니버셜 디스플레이 코포레이션 지연 형광 ｏｌｅｄ
US20140110698A1 (en) * 2010-06-11 2014-04-24 Universal Display Corporation Emitter materials for oleds
JP2016102132A (ja) * 2010-06-11 2016-06-02 ユニバーサル ディスプレイ コーポレイション 遅延蛍光ｏｌｅｄ
US9543532B2 (en) * 2010-06-11 2017-01-10 Universal Display Corporation Organic electroluminescent materials and devices
CN106432352A (zh) * 2010-06-11 2017-02-22 通用显示公司 延迟荧光oled
KR101873072B1 (ko) * 2010-06-11 2018-06-29 유니버셜 디스플레이 코포레이션 지연 형광 ｏｌｅｄ
KR101922393B1 (ko) 2010-06-11 2018-11-26 유니버셜 디스플레이 코포레이션 지연 형광 ｏｌｅｄ

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