EP1311520A1 - Carbenoide enthaltende rutheniumkomplexe - Google Patents
Carbenoide enthaltende rutheniumkomplexeInfo
- 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- Withdrawn
Links
- 150000003303 ruthenium Chemical class 0.000 title claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 42
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 6
- 125000000129 anionic group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 35
- -1 cyclic diaminocarbenes Chemical class 0.000 claims description 27
- 150000001336 alkenes Chemical class 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000005649 metathesis reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000001345 alkine derivatives Chemical class 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical class [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 238000010535 acyclic diene metathesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005865 alkene metathesis reaction Methods 0.000 description 3
- 238000005686 cross metathesis reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000005872 self-metathesis reaction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
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
Description
Claims
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 (de) | 2000-08-11 | 2001-08-10 | Carbenoide enthaltende rutheniumkomplexe |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1311520A1 true EP1311520A1 (de) | 2003-05-21 |
Family
ID=7652191
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01967261A Withdrawn EP1311520A1 (de) | 2000-08-11 | 2001-08-10 | Carbenoide enthaltende rutheniumkomplexe |
Country Status (11)
Country | Link |
---|---|
US (1) | US20030195357A1 (de) |
EP (1) | EP1311520A1 (de) |
JP (1) | JP2004506644A (de) |
KR (1) | KR20030022888A (de) |
CN (1) | CN1447815A (de) |
AU (1) | AU2001287677A1 (de) |
CA (1) | CA2419368A1 (de) |
DE (1) | DE10039389A1 (de) |
EA (1) | EA200300260A1 (de) |
MX (1) | MXPA03001161A (de) |
WO (1) | WO2002014336A1 (de) |
Families Citing this family (6)
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 (en) * | 2009-10-29 | 2011-05-19 | Board Of Regents, The University Of Texas System | Ruthenium-alkylidenes containing acyclic diaminocarbenes for obtaining low e/z ratios in cross metathesis |
Family Cites Families (3)
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 |
-
2000
- 2000-08-11 DE DE10039389A patent/DE10039389A1/de not_active Withdrawn
-
2001
- 2001-08-10 MX MXPA03001161A patent/MXPA03001161A/es unknown
- 2001-08-10 US US10/344,367 patent/US20030195357A1/en not_active Abandoned
- 2001-08-10 CA CA002419368A patent/CA2419368A1/en not_active Abandoned
- 2001-08-10 CN CN01814516A patent/CN1447815A/zh active Pending
- 2001-08-10 EA EA200300260A patent/EA200300260A1/ru unknown
- 2001-08-10 JP JP2002519473A patent/JP2004506644A/ja not_active Withdrawn
- 2001-08-10 KR KR10-2003-7001939A patent/KR20030022888A/ko not_active Application Discontinuation
- 2001-08-10 AU AU2001287677A patent/AU2001287677A1/en not_active Abandoned
- 2001-08-10 WO PCT/EP2001/009295 patent/WO2002014336A1/de not_active Application Discontinuation
- 2001-08-10 EP EP01967261A patent/EP1311520A1/de not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO0214336A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2002014336A1 (de) | 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 (en) | 2003-02-10 |
AU2001287677A1 (en) | 2002-02-25 |
US20030195357A1 (en) | 2003-10-16 |
KR20030022888A (ko) | 2003-03-17 |
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