WO1997011955A1 - Procede de preparation de complexes mononucleaires de ruthenium - Google Patents
Procede de preparation de complexes mononucleaires de ruthenium Download PDFInfo
- Publication number
- WO1997011955A1 WO1997011955A1 PCT/EP1996/004077 EP9604077W WO9711955A1 WO 1997011955 A1 WO1997011955 A1 WO 1997011955A1 EP 9604077 W EP9604077 W EP 9604077W WO 9711955 A1 WO9711955 A1 WO 9711955A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- dcbh
- complex
- excess
- acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000003303 ruthenium Chemical class 0.000 title 1
- 239000003446 ligand Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- GIDBEKINLBHYLA-UHFFFAOYSA-I pentachlororuthenium Chemical compound Cl[Ru](Cl)(Cl)(Cl)Cl GIDBEKINLBHYLA-UHFFFAOYSA-I 0.000 claims description 2
- JLMNFWCOAJFSHD-UHFFFAOYSA-I pentachlororuthenium hydrate Chemical compound O.Cl[Ru](Cl)(Cl)(Cl)Cl JLMNFWCOAJFSHD-UHFFFAOYSA-I 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 230000003595 spectral effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 3
- RROSXLCQOOGZBR-UHFFFAOYSA-N sodium;isothiocyanate Chemical compound [Na+].[N-]=C=S RROSXLCQOOGZBR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- 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
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
Definitions
- the present invention refers to a process for the preparation of mononuclear compounds of general formula (I) and (II)
- the above said complex is obtained by reaction of RuClo hydrate , commercially available , with dcbH 2 . in organic solvents , as for example DMF, at boiling point. Although the reaction itself runs with good yield, the quantity of final product obtained is limited because of the low solubility of the ligand dcbH 2 and, moreover, the process involves the use of toxic organic solvent with the related problems.
- the object of the present invention is a process for the preparation of mononuclear compounds of general formula (I) and (II)
- Y is a bi-dentate ligand wherein : a) a pentachlororuthenium complex or ruthenium trichloride hydrate is reacted with an excess of potassium or sodium oxalate b) the mixture of step (a) is added with an excess of 4,4'dicarboxy-
- 2,2-bipyridine in the form of sodium or potassium salt, in order to obtain the complex Ru(deb) - > (C 2 0 / !) c) the complex of step (b) is reacted with an excess of mono-dentate ligand (X) or bi-dentate ligand (Y) d) the final product is precipitated by adding acid.
- the present invention allows to overcome the above said problems by a process comprising as reaction-intermediate the complex
- the complex Ru(dcb) 2 (C 2 0 * j ) can be prepared by various methods. Examples of such methods are reported hereinafter.
- the sodium or potassium salt of 4,4'-dicarboxy-2,2'-bipyridine (Na 2 dcb or K 2 dcb) is added and let react in order to obtain the complex Ru(dcb) 2 (C 2 0* ) 4" ; the complex Ru(dcbH ) 2 ( C 0 4 ⁇ ) is thereafter precipitated by adding an acid, preferably HClOi, and isolated.
- the obtained complex is dissolved in water by adding NaOH up to neutrality and reacted for 3"6 hours, preferably 4 hours, with an appropriated excess of mono-dentate ligand (X) or bi-dentate ligand (Y), at 60° - 100 ⁇ C, preferably 80"C, and the final product is precipitated by adding an acid.
- ruthenium trichloride Ru(Cl) hydrate commercially available, is reacted at reflux temperature in aqueous solution with an excess (3-6 folds, preferably 4 folds) of sodium or potassium oxalate in the presence of ethyl alcohol.
- the ligand Na 2 dcb or K 2 dcb is added, preferably 50°C and drop by drop, and the mixture is heated at 60° - 100'C, preferably
- mono-dentate ligand means, for example, an halide, thiocyanate (NCS ⁇ ), cyanide CN " etc.
- bi-dentate ligand means, for example, polypyridine, dithiocarbamate, alpha'-bipyridine possibly substituted. 1,10-phenanthroline, ethylenediamine, etc..
- the solution containing the complex prepared as above described is directly reacted with 22 g Na dcb for 4 h at 80 ⁇ C and thereafter with 44 g NaNCS at 80°C for 4 h.
- the product is finally isolated by adding acid.
- the solid is dissolved in acetone and the solution filtered and dried on rotating evaporator.
- 19 g of Ru(dcbH ) (NCS) 2 are obtained, corresponding to the total conversion of ruthenium trichloride into the final product with a yield of 70%.
- EXAMPLE 10 g of RuClo are reacted with 27 g of potassium oxalate in 300 ml distilled water.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
L'invention concerne un procédé de préparation de colorants inorganiques, utiles comme sensibilisateurs spectraux pour les semi-conducteurs, dans lequel on utilise l'intermédiaire Ru(dcb)2(C2O4)-4.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU71305/96A AU7130596A (en) | 1995-09-26 | 1996-09-18 | Method of preparation of mononuclear ruthenium complexes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT95MI001979A IT1277655B1 (it) | 1995-09-26 | 1995-09-26 | Processo per la preparazione di coloranti inorganici ed intermedi di reazione in detto processo |
ITMI95A001979 | 1995-09-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997011955A1 true WO1997011955A1 (fr) | 1997-04-03 |
Family
ID=11372280
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/004077 WO1997011955A1 (fr) | 1995-09-26 | 1996-09-18 | Procede de preparation de complexes mononucleaires de ruthenium |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU7130596A (fr) |
IT (1) | IT1277655B1 (fr) |
WO (1) | WO1997011955A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999050358A1 (fr) * | 1998-03-27 | 1999-10-07 | Hahn-Meitner-Institut Berlin Gmbh | Photosensibilisateur destine a des applications industrielles solaires, son procede de production et configuration correspondante |
EP1049117A2 (fr) | 1999-04-26 | 2000-11-02 | Fuji Photo Film Co., Ltd. | Colorant de complexes métalliques pour des cellules photoélectrochimiques |
EP1178084A1 (fr) * | 2000-07-31 | 2002-02-06 | Neomat S.A. | Procédés de préparation de colorants et d'intermédiaires complexes du ruthénium avec des carboxylates et phosphonates de polypyridines |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994004497A1 (fr) * | 1992-08-21 | 1994-03-03 | Ecole polytechnique fédérale de Lausanne (EPFL) | Composes organiques |
-
1995
- 1995-09-26 IT IT95MI001979A patent/IT1277655B1/it active IP Right Grant
-
1996
- 1996-09-18 WO PCT/EP1996/004077 patent/WO1997011955A1/fr active Application Filing
- 1996-09-18 AU AU71305/96A patent/AU7130596A/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994004497A1 (fr) * | 1992-08-21 | 1994-03-03 | Ecole polytechnique fédérale de Lausanne (EPFL) | Composes organiques |
Non-Patent Citations (4)
Title |
---|
ARGAZZI R ET AL: "Enhanced Spectral Sensitivity from Ruthenium(II) Polypyridyl Based Photovoltaic Devices", INORG. CHEM. (INOCAJ,00201669);94; VOL.33 (25); PP.5741-9, CNR;CENTRO DI STUDIO SU FOTOREATTIVITA E CATALISI; FERRARA; 44100; ITALY (IT), XP000612748 * |
BENSON E P ET AL: "Ruthenium(II) azophenol and azonaphthol complexes", INORG. CHEM. (INOCAJ,00201669);81; VOL.20 (8); PP.2504-7, WASHINGTON STATE UNIV.;DEP. CHEM.; PULLMAN; 99164; WA; USA, XP002022619 * |
BIGNOZZI C A ET AL: "Bis(bipyridine)ruthenium(II) cyano-bridged polymeric cations", INORG. CHIM. ACTA (ICHAA3,00201693);84; VOL.86 (2); PP.133-6, UNIV. FERRARA;IST. CHIM.; FERRARA; 44100; ITALY (IT), XP000613457 * |
DEMAS J N ET AL: "Preparation and thin-layer chromatography of cis-dicyanobis(2,2'-bipyridine)ruthenium(II)", INORG. CHEM. (INOCAJ);69; VOL.8 (3); PP.674-5, WASHINGTON STATE UNIV.;PULLMAN; WASH., XP000615837 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999050358A1 (fr) * | 1998-03-27 | 1999-10-07 | Hahn-Meitner-Institut Berlin Gmbh | Photosensibilisateur destine a des applications industrielles solaires, son procede de production et configuration correspondante |
EP1049117A2 (fr) | 1999-04-26 | 2000-11-02 | Fuji Photo Film Co., Ltd. | Colorant de complexes métalliques pour des cellules photoélectrochimiques |
EP1049117A3 (fr) * | 1999-04-26 | 2005-03-23 | Fuji Photo Film Co., Ltd. | Colorant de complexes métalliques pour des cellules photoélectrochimiques |
EP1178084A1 (fr) * | 2000-07-31 | 2002-02-06 | Neomat S.A. | Procédés de préparation de colorants et d'intermédiaires complexes du ruthénium avec des carboxylates et phosphonates de polypyridines |
WO2002010286A3 (fr) * | 2000-07-31 | 2007-10-18 | Neomat S A | Procede de preparation de colorants a base de rhutenium polypyridine de carboxylate et de phosphonate et procede de preparation d'intermediaires de reaction utilises dans ce procede |
Also Published As
Publication number | Publication date |
---|---|
ITMI951979A1 (it) | 1997-03-26 |
IT1277655B1 (it) | 1997-11-11 |
AU7130596A (en) | 1997-04-17 |
ITMI951979A0 (fr) | 1995-09-26 |
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