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  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3932—Inorganic compounds or complexes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
  • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
  • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/2208—Oxygen, e.g. acetylacetonates
  • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
  • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
  • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/2208—Oxygen, e.g. acetylacetonates
  • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
  • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
  • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
• • 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
  • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
  • C07F13/005—Compounds without a metal-carbon linkage
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0213—Complexes without C-metal linkages
  • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
  • B01J2531/72—Manganese
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts

Definitions

• the present invention concerns novel manganese (II) carboxylate complexes, processes for their preparation and their use as disproportionation catalysts. More specifically, the novel complexes of the present invention are mono-, di- and poly- carboxylate complexes of manganese (II) which may, optionally, contain nitrogen and/or oxygen donor ligands. The present invention also concerns the use of the said complexes as catalysts for the disproportionation of hydrogen peroxide or the like hydrogen peroxide-liberating or generating percompounds.
• novel complexes of the invention have advantages over other known manganese complexes that have been employed as peroxide disproportionation catalysts in that (i) they are easily synthesised from cheap, readily available starting materials and (ii) they are extremely reactive towards hydrogen peroxide.
• Y is selected from the group comprising hydrogen, substituted or unsubstituted lower (C-*__2o) alkyl, substituted or unsubstituted lower ( 2-2O ' alkenyl, substituted or unsubstituted lower (C2-20) alkynyl, substituted or unsubstituted mono-, bi- or polycyclic saturated or unsaturated carbocyclic ring system, substituted or unsubstituted mono-, bi- or polycyclic aromatic hydrocarbon or substituted or unsubstituted mono-, bi- or polycyclic saturated or unsaturated heterocyclic ring system and, when p is 2, Y additionally is selected from the group comprising substituted or unsubstituted lower (C-j__20 ⁇ alkylene, substituted or unsubstituted lower (C2-20*' alkenylene or substituted or unsubstituted lower (
• Y is substituted by halogen, hydroxyl, lower ( -j__2o) alkoxy, nitro, a substituted or unsubstituted mono-, bi- or polycyclic saturated or unsaturated carbocyclic ring system, a substituted or unsubstituted mono-, bi- or polycyclic aromatic hydrocarbon or a substituted or unsubstituted mono-, bi- or polycyclic saturated or unsaturated heterocyclic ring system.
• Y is a carbocyclic ring system selected from the group comprising lower (C3_2o ⁇ cycloalkyl or a mono-, bi- or polyunsaturated derivative thereof, a fused bi- or polycyclic ring system, a bridged bi- or polycyclic ring system, optionally selected from bi- and polycyclic terpenes, and a bi- or polyspiro ring system.
• the terpene is norbornene.
• Y is a substituted or unsubstituted mono-, bi- or polycyclic aromatic hydrocarbon, preferably Cg_*j_2 aryl, optionally selected from phenyl, benzyl, naphthalenyl and anthracenyl, Y being optionally ' substituted by halogen, hydroxyl, lower (C]__2 ⁇ ) alkoxy or nitro.
• Y is naphthalenyl or 2-hydroxy-l- phenyl or, alternatively, Y is (C]__-*_o) lower alkylene, optionally selected from dimethylene, trimethylene, tetramethylene, pentamethylene and hexamethylene; p is 2; and m and q are each 0.
• Y is lower (C2- 10 ) alkenyl substituted by halogen, hydroxyl, lower (C-*__2o) alkoxy, nitro, a substituted or unsubstituted mono-, bi- or polycyclic saturated or unsaturated carbocyclic ring system, a substituted or unsubstituted mono-, bi- or polycyclic aromatic hydrocarbon or a substituted or unsubstituted mono-, bi- or polycyclic saturated or unsaturated heterocyclic ring system. More preferably Y is a lower (C 2 -1 0 ) alkenyl, optionally acrylyl, substituted by a heterocyclic ring system, most preferably imidazol-4-yl.
• the Mn(II) carboxylate complex additionally comprises at least one nitrogen donor ligand selected from substituted or unsubstituted saturated or unsaturated ring nitrogen-containing mono-, bi-, or polycyclic ring systems, ammonia, substituted or unsubstituted primary, secondary and tertiary amines or bi- or polycyclic fused ring systems .
• nitrogen donor ligand selected from substituted or unsubstituted saturated or unsaturated ring nitrogen-containing mono-, bi-, or polycyclic ring systems, ammonia, substituted or unsubstituted primary, secondary and tertiary amines or bi- or polycyclic fused ring systems .
• the nitrogen donor ligand is selected from substituted or unsubstituted pyridine, 1, 10-phenanthroline and 2, 2 ' -bipyridine.
• the Mn(II) carboxylate complex additionally comprises at least one oxygen donor ligand optionally selected from water, hydronium ions and lower (C-j__2 ⁇ ) alkanols, preferably ethanol .
• a process for the preparation of a Mn(II) carboxylate complex as defined hereinabove which process comprises reacting a Mn(II) salt of the formula
• L is a leaving group which may optionally be selected from acetate and halogen, preferably chloride, with an appropriate carboxylic acid, or a salt thereof, in a suitable reaction medium, preferably selected from water or an ethanol :water mixture, more preferably a 4:1 (v:v) ethanol :water mixture, to obtain the Mn(II) carboxylate complex.
• a suitable reaction medium preferably selected from water or an ethanol :water mixture, more preferably a 4:1 (v:v) ethanol :water mixture
• a catalyst for accelerating the disproportionation of hydrogen peroxide, hydrogen peroxide-liberating percompounds and hydrogen peroxide-generating percompounds comprising a Mn(II) carboxylate complex as defined hereinabove.
• carboxylate when used in the expressions "Mn(II) carboxylate complex” and "Mn(II) -carboxylate-nitrogen donor complex” and the like expressions is intended to embrace mono-, bi- and poly-carboxylate complexes.
• hydroxogen peroxide percompound is intended to embrace alkali metal peroxides, as well as alkali metal perborates, percarbonates, perphosphates and persulphates.
• a simple manganese (II) salt eg. manganese (II) acetate tetrahydrate or manganese (II) chloride tetrahydrate
• an excess of the appropriate carboxylic acid or the sodium salt of the acid
• water or an ethanol.-water mixture (4:1) (v:v) to give a suspension (or a solution) of the respective manganese (II) carboxylate complex in high yield.
• This manganese (II) carboxylate complex may then be added to a solution of a selected nitrogen donor base (N-base) to give the respective manganese (II) carboxylate/N-base complex in good yield.
• a simple manganese (II) salt eg. manganese (II) acetate tetrahydrate or manganese (II) chloride tetrahydrate
• an excess of the appropriate carboxylic acid or the sodium salt of the acid
• water or an ethanol :water mixture (4:1) (v:v) containing the dissolved nitrogen donor base (N-base) e.g., water or an ethanol :water mixture (4:1) (v:v) containing the dissolved nitrogen donor base (N-base) .
• the respective manganese (II) carboxylate/N-base complex is isolated in good yield.
• odaH2 octanedioic acid
• salH2 salicylic acid
• ndaH2 cis-5-norbornene-endo-2, 3-dicarboxylic acid
• bdoaH2 benzene-1, 2-dioxyacetic acid
• bndaH2 1, 1 ' -binaphtho-2, 2 ' -diacetic acid
• bdaH2 butanedioic acid
• phen 1, 10-phenanthroline
• py pyridine
• bipy 2, 2 ' -bipyridine
• E-uro E-urocanic acid (E-4-imidazole acrylic acid) .
• Example 1 Mn(oda) .H2 ⁇ (Complex 1) Mn(CH 3 C0 2 ) 2* 4 H2 ⁇ (1-0 g, 4.08 mmol) and octanedioic acid (0.825 g, 4.74 mmol) were refluxed together in an ethanol:water mixture (4:1) (100 ml) for 2 h. The white product (1) was filtered off, washed with ethanol and then air-dried. Yield 76%. Calc: C, 39.19; H, 5.76.
• IR (Csl matrix) 3580, 3520, 3060, 1600, 1490, 1440, 1390, 1350, 1240, 1150, 1030, 1020, 850, 760, 705, 660, 570, 540, 470, 390 cm" 1 .
• Complex (5) was readily soluble in aqueous ethanol, hot water and hot ethanol.
• IR Csl matrix
• Complex (8) readily dissolves in water and in warm ethanol .
• Example 12 [Mn(bnda) (phen)2 (H2O)2] (Complex 12) To a suspension of complex (11) (0.5 g, 0.98 mmol) in an ethanol :water mixture (4:1) (100 ml) was added 1, 10-phenanthroline (1.2 g, 6.67 mmol) . The resulting mixture was then refluxed for 2 hours. Upon cooling the light-green solution was filtered and, on standing for several days, green crystals of the product formed. The solid was filtered off, washed with ice-cold ethanol and then air-dried at ca 20°C. Calc: C, 67.79; H, 4.23; N. 6.58.
• This complex comprises a dimanganese (II, II) dianion and a dimanganese (II, II) dication.
• dianion [Mn2 (oda) 3 (phen) 4] 2"
• An oda 2- ligand bridges the two metals by using one carboxylate oxygen from each end of the dicarboxylate ligand.
• a monodentate oda 2- ligand is coordinated to each metal via a single carboxylate oxygen, and this is in a cis position with respect to the bridging carboxylate oxygen. The three remaining oxygen atoms of this oda 2" ligand remain uncoordinated.
• each Mn(II) atom is at the centre of a distorted N 4 O2 octahedron.
• the structure of the dication [Mn2 (oda) (phen) 4 (H2O) 2] 2+ is basically similar to that of the dianion in that each of the two symmetry related Mn(II) atoms has a distorted octahedral 4 O2 coordination geometry.
• Each metal is surrounded by two chelating phen groups and one carboxylate oxygen atom from the bridging oda 2 " ligand.
• the sixth coordination site is occupied by the oxygen atom of a water molecule which, again, is in a cisoid position with respect to the coordinated carboxylate oxygen atom of the bridging oda 2 " ligand.
• the complex comprises two associated and symmetry related pseudo seven-coordinate Mn(II) centres.
• Each Mn is asymmetrically chelated by two salH " (HOC/5H 4 CO2 " ) ligands and, perpendicular to the central plane, there are two coordinated water molecules. Association of the two metals occurs via the carboxylate oxygen atoms from a second pair of chelating salH ⁇ ligands, effectively creating two asymmetric bridges between the Mn atoms.
• the stability of complex (3) in the solid state is further enhanced by intramolecular hydrogen bonding between the hydroxyl groups of the salH" function and one carboxylate oxygen of the same ligand. [ ⁇ Mn 2 ( sal ) 2 ( salH) ( H 2 0 ) (H 3 0) (py) 4 - 2py ⁇ n ] (Complex 4 )
• the complex comprises three independent Mn(II) atoms ⁇ Mnl, Mn2 and Mn3 ⁇ in a polymeric system of the type
• Mn2 lies on another inversion centre and it has an N 2 O 4 octahedral coordination geometry identical to that of Mnl.
• Mn3 is in a general position, and is bonded to the second carboxylate oxygen atom from the sal 2 " ligand which is coordinated to Mnl, and also to the second carboxylate oxygen atom from the sal 2 " ligand which is coordinated to Mn2.
• the coordination mode of the carboxylate moieties of both of these bridging sal 2 " ligands is syn-anti bidentate.
• the oxygen atom of a water molecule and the oxygen atom of a cisoid hydronium ion (H 3 0 + : oxygen donor ligand) are also coordinated to Mn3, and the N2O octahedral coordination about the metal is completed by two axial pyridine ligands.
• a salH" ion is hydrogen bonded via its carboxylate oxygens in a syn-syn bidentate bridging mode to the water molecule and to the hydronium ion which are coordinated to Mn3. Additional inter-ligand hydrogen bonding interactions are also present.
• the salicylate carboxylate groups each form asymmetric bridges to further manganese atoms, forming spiral chains parallel to the two-fold screw axis.
• the complex comprises a single manganese (II) atom in a distorted six-coordinate geometry.
• the metal is ligated by two chelating phenanthroline ligands and two carboxylate oxygen atoms (one from each of the two carboxylate functions on the nda 2" ligand) .
• the water molecule is hydrogen bonded to one of the free carbonyl oxygens of the nda 2 " ligand.
• the ethanol molecule is hydrogen bonded to this water molecule.
• the complex comprises a single seven-coordinate manganese (II) ion.
• the bdoa 2" acts as a chelating quadridentate ligand and is bound to the metal via the two ethereal oxygen atoms and two carboxylate oxygens, one from each end of the diacid. The remaining three coordination sites are occupied by the oxygen atoms of three water molecules. [Mn ( E-uro ) 2 (H 2 0) 4 ] ( Complex 14 )
• This complex shows two distinct isomers of [Mn(E-uro) 2 (H2O) 4] .
• One isomer has the imine nitrogen atom of the imidazole ring lying in a cisoid orientation with respect to the carbon-carbon double bond which bears the pendant carboxylate group, whilst in the other isomer the same nitrogen atom is transoid to the double bond.
• Both species are centrosymmetric, so that the asymmetric unit comprises two independent half molecules.
• the geometry at manganese is approximately octahedral, with the metal coordinated by the imine nitrogen atoms from two urocanate anions trans to one another, and also by four water molecules.
• the reaction flask was equipped with a magnetic stirring bar and thermostatted at 25°C.
• Solid complex (ca 10 mg) and solid imidazole (50 mg) were added to the flask, and then aqueous H2O2 (35% w/w, 10 ml, 114 mmol) was injected using a syringe.
• the resulting mixture was stirred, and the evolved O2 was measured volumetrically (ml) over a period of time (min) .
• the results are set out in Table 1 hereinbelow.
• Example 17 H2O2 Disproportionation Results for Complexes (2) and (8) .
• the reaction flask was equipped with a magnetic stirring bar and thermostatted at 25°C. Solid complex (ca 10 mg) was added to the flask, and then aqueous H2O2 (35% w/w, 5 ml, 57 mmol) was injected using a syringe. The resulting mixture was stirred, and the evolved O2 was measured volumetrically (ml) over a period of time (min) (see Table 2 annexed) .
• the complexes of the invention also catalyze the disproportionation of H2O2 in the absence of imidazole.
• Mn (II) carboxylate complexes of the present invention have been tested in contact with various stains such as tea, coffee and red wine. It is been shown, in these tests, that the complexes of the invention act as effective bleaching catalysts, either in the presence of a nitrogen donor ligand such as imidazole or 1, 10-phenanthroline or in the absence of a nitrogen donor ligand. Accordingly, Mn (II) carboxylate complexes of the present invention are suitable for use in surface cleaners and washing powders .

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• 1995
  • 1995-11-14 EP EP95938006A patent/EP0804444A1/de not_active Withdrawn
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