WO1997011955A1 - Method of preparation of mononuclear ruthenium complexes - Google Patents
Method of preparation of mononuclear ruthenium complexes Download PDFInfo
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- 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
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- 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
The invention refers to a process for the preparation of inorganic dyes, useful as spectral sensitizers for semiconductors, wherein the intermediate Ru(dcb)2(C2O4)4- is used.
Description
METHOD OF PREPARATION OF MONONUCLEAR RUTHENIUM COMPLEXES
Field of the invention
The present invention refers to a process for the preparation of mononuclear compounds of general formula (I) and (II)
Ru(dcbH2)2(X)2 (I)
Ru(dcbH2)2(Y) (II) wherein : dcbH2 is 4, -dicarboxy-2,2'-bipyridine; X is a mono-dentate ligand and Y is a bi-dentate ligand useful as inorganic dyes for the sensibilisation of semiconductors of type n, as for example titanium dioxide. Such dyes are used, for example, in photoelectrochemical regenerating cells based on nanocrystalline electrods of titanium dioxide. State of the art
In literature [see: M.Z.Nazeeruddin et al. J.Am.Chem.Soc. 1993. H5.
6382; Heimer T.A. et al. J.Phys.Chem. 1993, 97. 11987; Argazzi R. et al. Inorg. Chem. 199*4, 33. 57*^1] processes for the preparation of compounds of formula (I) and (II) as above said are described comprising, as reaction intermediate, the complex Ru(dcbH2)2(cl)2t or its deprotonated form Ru(dcb)2(Cl) , obtained by neutralisation of
Ru(dcbH2)(Cl)2.
The above said complex is obtained by reaction of RuClo hydrate , commercially available , with dcbH2. 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 dcbH2 and, moreover, the process involves the use of toxic organic solvent with the related problems.
Summary of the invention
The object of the present invention is a process for the preparation of mononuclear compounds of general formula (I) and (II)
Ru(dcbH2)2(X)2 (I)
Ru(dcbH2)2(Y) (II) wherein: dcbH2 is 4 ,4 ' -dicarboxy-2 , 2 ' -bipyridine X is a mono-dentate ligand
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) -> (C20/!) 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.
Detailed description of the invention
The present invention allows to overcome the above said problems by a process comprising as reaction-intermediate the complex
Ru(dcb) (C20*j) , wherein deb represents the bianionic form of the ligand 4. '-dicarboxy-2,2'-bipyridine. The process gives high yields allowing the preparation of high quantities of final compounds in aqueous solution and in mild reaction conditions.
The process according to the present invention can be represented by the following reactions:
Ru(dcb)2(C20il)Z|" + 2 X" > Ru(dcb)2(X)2 i+"
Ru(dcb)2(X)2 i|" + 4 H+ > Ru(dcbH2)(X)2 The complex Ru(dcb)2(C20* j) can be prepared by various methods. Examples of such methods are reported hereinafter.
The synthesis of the intermediate Ru(dcb) (C20* |) puts no limit to the production of the wanted dyes; it can in fact be prepared in high quantities with high yield. Moreover, such intermediate can be prepared in aqueous solution and in mild conditions. According to an embodiment of the present invention the commercial product pentachlororuthenium hydrate K2Ru(Cl)c is reacted in water with an excess (10-30 folds, preferably 20 folds) of sodium- or potassium- oxalate at 60β - 100'C, preferably 80*C. The sodium or potassium salt of 4,4'-dicarboxy-2,2'-bipyridine (Na2dcb or K2dcb) is added and let react in order to obtain the complex Ru(dcb)2(C20* )4"; the complex Ru(dcbH )2 ( C 04ι ) 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° - 100βC, preferably 80"C, and the final product is precipitated by adding an acid. According to a different embodiment of the invention 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 Na2dcb or K2dcb is added, preferably 50°C and drop by drop, and the mixture is heated at 60° - 100'C, preferably
80βC.
At this point two different reaction-pathways can be followed: -(1) the complex Ru(dcbH2)2(C2θ4) is isolated by adding an acid, preferably perchloric acid, and thereafter reacted with an excess of the mono-dentate ligand (X) or bi-dentate ligand (Y) as described above; or -(2) an excess of mono-dentate ligand (X) or bi-dentate ligand (Y) is added directly in the solution and the heating is continued for some hours at 60β-100*C, preferably 8θ"C; the product is thereafter precipitated by adding an acid.
In the present invention 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 invention will be better understood in the light of the following examples. EXAMPLE 1
10 g of K2Ru(Cl)c hydrate are reacted for 1 hour with 100 g of potassium oxalate and 15 g. of the sodium salt of 4,4'-dicarboxy-2,2'- bipyridine (Na dcb) in 600 ml distilled water at 80°C. The solution is acidified and 15 g of Ru(dcbH2)2(C^) precipitate (yield 83 ). The product is neutralized with NaOH and dissolved in 500 ml of distilled water.
37 g of NaNCS are added and reacted at 75*C for 4 h. Acid is added up
to the total precipitation of product. The solid is dissolved in acetone and the solution is filtered and dried on rotating evaporator. According to the above described procedure 14 g of Ru(dcbH2)2(NCS)2 are obtained, corresponding to the conversion of Ru(dcbH )2(C20^) into the final product with a yield of 90 . EXAMPLE 2
10 g of RuCl hydrate are reacted with 27 g of potassium oxalate in 300 ml distilled water. To the solution 0 ml of ethyl alcohol are added and the mixture is refluxed for 4 h. This procedure permits to obtain the complex which can be isolated or directly
reacted in the same aqueous solution with 22 g Na2dcb, for 4 h at 80βC. The adding of an acid to the reaction mixture allows to obtain 19 g of the intermediate Ru(dcbH2)2(C20*j) (yield 73 ). The product can be converted, for example, in Ru(dcbH2)2(NCS)2 as described in Example 1.
Alternatively, the solution containing the complex
prepared as above described, is directly reacted with 22 g Na dcb for 4 h at 80βC 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. By this procedure 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. To the solution 60 ml of ethyl alcohol are added and the solution is refluxed for 4 h. The reaction mixture is cooled to
room temperature and pH adjusted to 7 by adding NaOH IM. The reaction mixture is heated to 50°C and a solution containing 22 g of Na?dcb in 350 ml of distilled water is added thereto. The addition is performed drop by drop in 2 hours. The reaction mixture is heated to 70βC and let react for 2 more hours. The solution is cooled to room temperature and filtered.
To the filtered solution 700 ml of HC10/j 2M are added under stirring. The precipitate is separated by centrifugation and washed twice with 300 ml HClO-j 0.5 M (each). The precipitate is suspended in 300 ml acetone/ether (3:1) and the stirring maintained for 15 minutes.
The above said procedure permits to obtain 22 g of oxalate-complex Ru(dcbH2)2(C 0/j) (yield 84%). The product is converted in the dye Ru(dcbH)2(NCS)2 as described hereinafter. 22 gr of Ru(dcbH)2(C20/) are dissolved in 500 ml distilled water by adding NaOH IM up to pH 1.
50 g of NaNCS are added to the solution and the mixture kept at 70°C for 4 h. The mixture is cooled to room temperature and HCl 2M is added up to pH 1-1.5 under stirring. The precipitate is collected by centrifugation and resuspended in HCl IM under stirring for 30 minutes. The step is repeated twice until the eentrifugated solution is pale yellow or almost colourless.
The precipitate, Ru(dcbH2)2(NCS)2 is eentrifugated. dissolved in acetone and the solution is filtered and evaporated in rotating evaporator. 22 g of Ru(dcbH2)2(020*4)2 are obtained (yield 95% calculated on Ru(dcbH2)2(C20ii)).
Claims
CLAIMS 1. Process for the preparation of mononuclear compounds of general formula (I) and (II) Ru(dcbH2)2(X)2 (I) Ru(dcbH2)2(Y) (II) wherein: dcbH2 is 4,4'-dicarboxy-2,2'-bipyridine X is a mono-dentate ligand 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(dcb)2(C20* )4" 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. 2. Process according to claim 1, wherein a pentachlororuthenium hydrate complex is used as starting product. 3- Process according to claim 2, wherein the step (a) is performed in aqueous solution at 60"-100"C, preferably 8θβC. 4. Process according to claim 3. wherein the complex obtained in step (b) is precipitated by adding an acid, isolated, purified. 5- Process according to claim 4, wherein the step (c) is performed in aqueous solution at βO'-lOO'C, preferably 80eC. 6. Process according to claim 1, wherein ruthenium trichloride hydrate
is used. 7- Process according to claim 6, wherein the step (a) is performed in aqueous solution in the presence of ethyl alcohol at reflux temperature . 8. Process according to claim 7. wherein the addition of 4,4'- dicarboxy-2,2'-bipyridine in step (b) is performed at 50βC and drop by drop. 9- Process according to claim 8, wherein step (c) is performed by adding the excess of ligand directly in the mixture obtained from previous step (b). 10. Process according to claims 1-9. wherein the acid used for precipitating the complexes in step (b) is perchloric acid.
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 |
|---|---|---|---|
| ITMI95A001979 | 1995-09-26 | ||
| IT95MI001979A IT1277655B1 (en) | 1995-09-26 | 1995-09-26 | PROCESS FOR THE PREPARATION OF INORGANIC DYES AND REACTION INTERMEDIATES IN THE SAID PROCESS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1997011955A1 true WO1997011955A1 (en) | 1997-04-03 |
Family
ID=11372280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1996/004077 WO1997011955A1 (en) | 1995-09-26 | 1996-09-18 | Method of preparation of mononuclear ruthenium complexes |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU7130596A (en) |
| IT (1) | IT1277655B1 (en) |
| WO (1) | WO1997011955A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999050358A1 (en) * | 1998-03-27 | 1999-10-07 | Hahn-Meitner-Institut Berlin Gmbh | Photosensitizer for applications in solar technology, method for the production thereof and configuration to implement the method |
| EP1049117A2 (en) | 1999-04-26 | 2000-11-02 | Fuji Photo Film Co., Ltd. | Metal complex dye for a photoelectrochemical cell |
| EP1178084A1 (en) * | 2000-07-31 | 2002-02-06 | Neomat S.A. | Processes for the preparation of carboxylate and phosphonate ruthenium polypyridine dyes and intermediates |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994004497A1 (en) * | 1992-08-21 | 1994-03-03 | Ecole polytechnique fédérale de Lausanne (EPFL) | Organic compounds |
-
1995
- 1995-09-26 IT IT95MI001979A patent/IT1277655B1/en active IP Right Grant
-
1996
- 1996-09-18 AU AU71305/96A patent/AU7130596A/en not_active Abandoned
- 1996-09-18 WO PCT/EP1996/004077 patent/WO1997011955A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994004497A1 (en) * | 1992-08-21 | 1994-03-03 | Ecole polytechnique fédérale de Lausanne (EPFL) | Organic compounds |
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 (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999050358A1 (en) * | 1998-03-27 | 1999-10-07 | Hahn-Meitner-Institut Berlin Gmbh | Photosensitizer for applications in solar technology, method for the production thereof and configuration to implement the method |
| EP1049117A2 (en) | 1999-04-26 | 2000-11-02 | Fuji Photo Film Co., Ltd. | Metal complex dye for a photoelectrochemical cell |
| EP1049117A3 (en) * | 1999-04-26 | 2005-03-23 | Fuji Photo Film Co., Ltd. | Metal complex dye for a photoelectrochemical cell |
| EP1178084A1 (en) * | 2000-07-31 | 2002-02-06 | Neomat S.A. | Processes for the preparation of carboxylate and phosphonate ruthenium polypyridine dyes and intermediates |
| WO2002010286A2 (en) * | 2000-07-31 | 2002-02-07 | Neomat S.A. | Process for the preparation of carboxylate and phosphonate ruthenium polypyridine dyes and a process for the preparation of reaction intermediates used in such process |
| WO2002010286A3 (en) * | 2000-07-31 | 2007-10-18 | Neomat S A | Process for the preparation of carboxylate and phosphonate ruthenium polypyridine dyes and a process for the preparation of reaction intermediates used in such process |
Also Published As
| Publication number | Publication date |
|---|---|
| ITMI951979A1 (en) | 1997-03-26 |
| IT1277655B1 (en) | 1997-11-11 |
| AU7130596A (en) | 1997-04-17 |
| ITMI951979A0 (en) | 1995-09-26 |
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