EP2739631A1 - Complexes homoleptiques terre rare/trisaryle - Google Patents

Complexes homoleptiques terre rare/trisaryle

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Publication number
EP2739631A1
EP2739631A1 EP12750525.3A EP12750525A EP2739631A1 EP 2739631 A1 EP2739631 A1 EP 2739631A1 EP 12750525 A EP12750525 A EP 12750525A EP 2739631 A1 EP2739631 A1 EP 2739631A1
Authority
EP
European Patent Office
Prior art keywords
rare earth
reaction
homoleptic
complexes
trisaryl
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Withdrawn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
EP12750525.3A
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German (de)
English (en)
Inventor
Oliver Thomas
Jörg SUNDERMEYER
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.)
Albemarle Germany GmbH
Original Assignee
Rockwood Lithium GmbH
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Filing date
Publication date
Application filed by Rockwood Lithium GmbH filed Critical Rockwood Lithium GmbH
Publication of EP2739631A1 publication Critical patent/EP2739631A1/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Withdrawn legal-status Critical Current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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5345—Complexes or chelates of phosphine-oxides or thioxides with metallic compounds or metals
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/535—Organo-phosphoranes
    • C07F9/5352—Phosphoranes containing the structure P=C-
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/08—Isoprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F36/08—Isoprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
    • C08F4/545—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams

Definitions

  • the invention relates to chelate-stabilized homoleptic trisaryl compounds based on
  • Phenylphosphoranes and methods for their preparation and their use as catalysts are described.
  • Figure 1 The tppo ligand and its cyclometallated variant.
  • Figure 3 tppo compounds of middle and later transition metals.
  • [Cp * 2 Sm (tppo)] can be obtained as a molecular stable compound.
  • Figure 6 Decomposition reaction of the lithiated triphenylmethylidene phosphorane.
  • the object of the invention is to provide novel homoleptic rare earth trisaryl complexes, to provide processes for the preparation of such complex compounds and to test their properties.
  • R 1 , R 2 phenyl
  • X O
  • SE Sc, Y, Lu or Yb in the homoleptic rare earth trisaryl complex.
  • X CH 2
  • SE Sc, Y, Lu, Sm, Gd or Dy.
  • the homoleptic rare earth trisaryl complex according to the invention is particularly preferably selected from the group consisting of:
  • the homoleptic rare earth trisaryl complexes of this invention are prepared by reacting a triphenyl phosphorane with a solvated rare earth metal halide or solvated organo-rare earth metal complex in the temperature range of -30 ° C to 120 ° C.
  • the reaction takes place as salt elimination and / or hydrocarbon elimination.
  • the process is carried out in situ as a one-pot reaction.
  • the reaction is carried out in aromatics, cyclic ethers or in mixtures of these solvents.
  • Figure 8 Possible synthetic routes to homoleptic rare earth metal complexes of ortho-metalated phenylphosphoranes.
  • the processes I-III described thus provide access to the new class of homoleptic chelate-stabilized phenylphosphorane complexes of the rare earths. It was possible to obtain the trivalent cations of the metals samarium, gadolinium, dysprosium, yttrium, ytterbium, lutetium and scandium using triphenylphosphoranes such as triphenylphosphine oxide or triphenylmethylidenephosphorane.
  • the reaction is particularly preferably carried out in the temperature range from 0 ° C to 60 ° C.
  • the triphenylphosphorane is reacted with a solvated rare earth metal halide or solvated organo-rare earth metal complex in a molar ratio of 3: 1.
  • an equimolar amount of a lithium base is added to the triphenylphosphorane feed.
  • the homoleptic rare earth-trisaryl complexes are used as reagents or catalysts for organic reactions, as catalysts for ring-opening polymerizations to produce polyesters.
  • the compounds show after a first screening catalytic activity in the ring-opening polymerization of ⁇ -caprolactone and after activation in the diene polymerization of isoprene.
  • DSC measurements and NMR spectroscopic analyzes showed a high proportion of the nature-identical 1,4-cis polyisoprene in the polymer.
  • the SCHLENK technique was used.
  • the glassware used was baked in a high vacuum and after the Cooling with argon 4.8 of the company AIR LIQUIDE filled.
  • the argon used for this purpose was dried by means of a P 4 O 10 granulate and subsequently filled with a Solvona ® column. Weighing and sample preparation for analytical investigations as well as the storage of oxygen- and / or hydrolysis-sensitive substances took place in glove boxes (type MB 150 BG-I, BRAUN, Lab Master 130, BRAUN) under a nitrogen atmosphere.
  • the data collection took place with the IPDS software X-Area of the company STOE.
  • the integration of the collected data was performed in the service department while the solving and refining itself was done.
  • Absorbance corrections were made semiempirically using multiscans, if possible.
  • Direct methods were used for the structural solution (Sir-92, Sir-97, Sir-2002, Sir-2004 and SHELXS-86).
  • SHELXL-97 the method of least squares was used (SHELXL-97). With the exception of the hydrogen atoms, the positions of all atoms were anisotropically refined. Hydrogen atoms attached to structure-forming
  • Crystal structure analyzes can be found in the crystallographic appendix.
  • thermogravimetric analysis was carried out on a device of the type TGA / SDTA 851 (METTLER TOLEDO).
  • TGA thermogravimetric analysis
  • the sample was weighed into a 70 pL alumina crucible by means of the integrated Ultra-Micro balance.
  • the DSC measurements of the polymer samples were carried out on a METTLER TOLEDO type DSC 821 e instrument.
  • 6 to 8 mg of the substance were each weighed into a 40 pL aluminum crucible.
  • a hole was made in the lid of the sealed crucible to ensure pressure equalization.
  • a temperature program with two cycles was used.
  • the samples were measured in a temperature range of -90 to 60 ° C at heating rates of 10 K / min.
  • IR spectroscopy (v / cm- 1 ): 3011 (br), 1483 (w), 1436 (s), 1415 (w), 1222 (w), 1 195 (w), 1131 (s), 1119 (s ), 1079 (s), 1063 (s), 1025 (m), 998 (m), 748 (w), 721 (s), 692 (s), 628 (s), 537 (s), 463 (s ), 443 (s), 414 (s).
  • Example 2 410 mg [YCl 3 (thf) 3 ] (1.0 mmol) were weighed together with 835 mg triphenylphosphine oxide (3.0 mmol) and 15 mL THP were added. The suspension was stirred for 30 minutes at room temperature. being from the einaanas finely crystalline substances a coarse flocculent solid formed. Subsequently, it was cooled to 0 ° C and treated with 1.5 mL of PhLi solution (20% solution in Bu 2 0, 3.0 mmol) and for a further two hours at a given
  • IR spectroscopy (v / cm- 1 ): 3024 (w, br), 2936 (w, br), 2844 (w, br), 1483 (w), 1435 (m), 1194 (w), 1131 (w ), 11 18 (m), 1080 (m), 1063 (w), 1047 (w), 1025 (w), 997 (w), 871 (w), 747 (w), 720 (m), 691 ( m), 627 (w), 537 (s), 460 (m), 449 (m).
  • Example 3 249 mg of [LuCl 3 (thf) 3 ] (0.5 mmol) were weighed together with 418 mg of triphenylphosphine oxide (1.5 mmol) and 10 ml of THP were added. The suspension was stirred at room temperature for 30 minutes, starting from the initially finely crystalline
  • IR spectroscopy (v / cm '1 ): 3011 (w, br), 1483 (w), 1436 (m), 1415 (w), 1222 (w), 1195 (w), 1131 (m), 1119 ( m), 1079 (m), 1063 (m), 1025 (w), 998 (w), 748 (w), 721 (m), 692 (m), 628 (w), 537 (s), 463 ( m), 443 (m), 414 (m).
  • Example 4 248 mg [YbCl 3 (thf) 3 ] (0.5 mmol) were weighed together with 418 mg triphenylphosphine oxide (1.5 mmol) and 10 mL THP were added. The suspension was stirred for 30 minutes at room temperature, forming a coarse flocculent solid from the initially fine crystalline substances. Subsequently, the mixture was cooled to 0 ° C. and treated with 0.75 ml of PhLi solution (20% strength solution in Bu 2 O, 1.5 mmol) and stirred for a further 2 hours
  • IR spectroscopy (v / cm -1 ): 3025 (w, br), 2926 (w, br), 2844 (w, br), 1483 (w), 1435 (m), 1194 (w), 1131 (w ), 1117 (m), 1082 (m), 1063 (w), 1047 (w), 1025 (w), 997 (w), 871 (w), 747 (w), 720 (m), 690 (m ), 627 (w), 537 (s), 460 (m), 446 (m).
  • Poly-e-caprolactone The polymerization of ⁇ -caprolactone was always carried out in toluene at room temperature.
  • the catalyst: monomer ratio was chosen to be 1: 150.
  • Living polymerization assay In the example of It should be shown that in the case of the ring-opening polymerization of ⁇ -caprolactone with this class of substance is a living polymerization. For this purpose, a starting ratio of catalyst: monomer of 1: 150 was selected.
  • Poly-L-lactide (A) The polymerization of L-lactide was always carried out in toluene at room temperature.
  • the catalyst: monomer ratio was chosen to be 1: 150.
  • Poly-L-lactide (B) 40,000 mg (0.05941 mmol, 1eq) were dissolved in 5.0 mL toluene and added to a solution of 2.569 g (LL) -dilactide (0.01782 mmol, 300 eq) in 10.0 mL toluene.
  • the reaction mixture was heated at 100 ° C for 24 hours. After this
  • reaction solution was poured into 200 ml of weakly HCl-acidic methanol, whereby the polymer precipitated. This was dried overnight at 40 ° C.
  • sample preparation for the GPC measurement was carried out by renewed dissolution in THF, followed by filtration through a 0.45 ⁇ m syringe filter and renewed precipitation in 100 ml of methanol cooled to 0.degree.
  • IR spectroscopy (v / cm '1 ): 2970 (w, br), 1433 (m), 1413 (w), 1102 (m), 1070 (m), 998 (w), 868 (m), 741 ( m), 720 (m), 690 (m), 665 (m), 625 (m), 520 (s), 491 (m), 455 (m), 433 (w), 404 (w).
  • Example 8 The synthesis was carried out on a scale of 0.5 mmol. The reaction time was 24 hours. After recrystallization, 322 mg (74%) of a yellow, finely crystalline solid were obtained.
  • IR spectroscopy (v / cm -1 ): 3020 (w, br), 2946 (w, br), 1480 (w), 1434 (m), 1414 (w), 1102 (m), 1073 (m), 1027 (w), 998 (w), 970 (w), 931 (w), 868 (m), 749 (m), 737 (s), 711 (m), 691 (s), 630 (m), 532 (m), 513 (s), 452 (s), 434 (m), 412 (m).
  • Example 9 The synthesis was carried out on a scale of 0.5 mmol. The reaction time was 24 hours. After recrystallization, 345 mg (69%) of the yellow, crystalline product were obtained.
  • IR spectroscopy (v / cm -1 ): 3011 (w, br), 2949 (w, br), 1434 (m), 1412 (w), 1174 (w), 1113 (w), 1099 (m), 1070 (m), 1027 (w), 998 (w), 979 (w), 927 (m), 868 (m), 730 (m), 712 (m), 691 (s), 627 (w), 558 (w), 512 (s, br), 464 (m), 447 (m), 408 (m).
  • Example 10 The synthesis was carried out on a scale of 0.5 mmol. The reaction time was six hours. After recrystallization, 351 mg (71%) of the desired product were isolated.
  • Example 11 The synthesis was carried out on a scale of 0.5 mmol. The reaction time was six hours. After recrystallization, 275 mg (56%) of the yellow, crystalline target compound were obtained.
  • Example 12 The synthesis was carried out on a scale of 0.5 mmol. The reaction time was three hours. After recrystallization, 376 mg (77%) of compound 13 were isolated.
  • IR spectroscopy (v / cm 1 ): 2969 (w, br), 1433 (m), 1130 (w), 1103 (m), 1069 (w), 1026 (w), 997 (w), 872 (m ), 741 (m), 721 (m), 691 (s), 656 (m), 624 (m), 517 (s), 490 (s), 454 (m), 431 (m), 414 (m ).
  • Poly- ⁇ -caprolactone The polymerization of ⁇ -caprolactone was always carried out in toluene at room temperature.
  • Table 5 Summary of the polymerization results of ⁇ -caprolactone.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Catalysts (AREA)
  • Polymerization Catalysts (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des composés trisaryles homoleptiques stabilisés par chélation, à base de phénylphosphoranes, ainsi que des procédés pour leur préparation et leur utilisation comme catalyseurs. Selon l'invention, l'objectif est atteint par des complexes homoleptiques terre rare/trisaryle de formule générale (1), dans laquelle SE = Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb ou Lu; X = O, CRR'; R1, R2 = phényle; R, R'= indépendamment l'un de l'autre H, alkyle avec n = 10 atomes de carbone, phényle ou triméthylsilyle.
EP12750525.3A 2011-08-02 2012-08-02 Complexes homoleptiques terre rare/trisaryle Withdrawn EP2739631A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011080285 2011-08-02
PCT/EP2012/003293 WO2013017281A1 (fr) 2011-08-02 2012-08-02 Complexes homoleptiques terre rare/trisaryle

Publications (1)

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EP2739631A1 true EP2739631A1 (fr) 2014-06-11

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US (1) US9187505B2 (fr)
EP (1) EP2739631A1 (fr)
JP (1) JP6000351B2 (fr)
KR (1) KR20140067022A (fr)
CN (1) CN103889992B (fr)
WO (1) WO2013017281A1 (fr)

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CN106478717B (zh) * 2016-09-27 2018-05-08 苏州大学 含三齿nnp配体的稀土金属受阻路易斯酸碱对的合成及其应用
CN110330637B (zh) * 2019-07-19 2021-04-20 大连理工大学 一类稀土大环内酯/戊内酯/己内酯三元共聚物及其制备方法

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DE19757524A1 (de) * 1997-12-23 1999-06-24 Bayer Ag eta-Komplex-Verbindungen
JP3668966B2 (ja) * 2001-09-07 2005-07-06 関西ティー・エル・オー株式会社 希土類錯体並びにそれを用いた光機能材料及び発光装置

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ANDREA L. WAYDA ET AL: "Homoleptic organolanthanoid hydrocarbyls. The synthesis and x-ray crystal structure of tris[o-((dimethylamino)methyl)phenyl]lutetium", ORGANOMETALLICS, vol. 3, no. 6, 1 June 1984 (1984-06-01), US, pages 939 - 941, XP055406944, ISSN: 0276-7333, DOI: 10.1021/om00084a023 *
O THOMAS: "Homoleptische tris-Aryl-Verbindungen des Yttriums", DIPLOMARBEIT, 1 January 2008 (2008-01-01), Marburg, pages 1 - 131, XP055375196, Retrieved from the Internet <URL:www> [retrieved on 20170523] *
PETROV A R ET AL: "Dramatic enhancement of the stability of rare-earth metal complexes with alpha-methyl substituted N,N-dimethylbenzylamine ligands", JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 695, no. 25-26, 1 December 2010 (2010-12-01), pages 2738 - 2746, XP027509636, ISSN: 0022-328X, [retrieved on 20100926], DOI: 10.1016/J.JORGANCHEM.2010.09.042 *
See also references of WO2013017281A1 *

Also Published As

Publication number Publication date
KR20140067022A (ko) 2014-06-03
US20140155562A1 (en) 2014-06-05
JP2014524412A (ja) 2014-09-22
CN103889992B (zh) 2016-08-31
CN103889992A (zh) 2014-06-25
WO2013017281A1 (fr) 2013-02-07
JP6000351B2 (ja) 2016-09-28
US9187505B2 (en) 2015-11-17

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