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WO1997011955A1 - Procede de preparation de complexes mononucleaires de ruthenium - Google Patents

Procede de preparation de complexes mononucleaires de ruthenium Download PDF

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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
Application number
PCT/EP1996/004077
Other languages
English (en)
Inventor
Carlo Alberto Bignozzi
Roberto Argazzi
Franco Scandola
Original Assignee
R.V.A. Capital Risque S.A.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by R.V.A. Capital Risque S.A. filed Critical R.V.A. Capital Risque S.A.
Priority to AU71305/96A priority Critical patent/AU7130596A/en
Publication of WO1997011955A1 publication Critical patent/WO1997011955A1/fr

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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
    • 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.
PCT/EP1996/004077 1995-09-26 1996-09-18 Procede de preparation de complexes mononucleaires de ruthenium WO1997011955A1 (fr)

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

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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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994004497A1 (fr) * 1992-08-21 1994-03-03 Ecole polytechnique fédérale de Lausanne (EPFL) Composes organiques

Patent Citations (1)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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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