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WO1996015136A1 - Nouveaux complexes de carboxylate de manganese (ii), leurs procedes de preparation et leur utilisation comme catalyseurs de dismutation - Google Patents

Nouveaux complexes de carboxylate de manganese (ii), leurs procedes de preparation et leur utilisation comme catalyseurs de dismutation Download PDF

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Publication number
WO1996015136A1
WO1996015136A1 PCT/IE1995/000059 IE9500059W WO9615136A1 WO 1996015136 A1 WO1996015136 A1 WO 1996015136A1 IE 9500059 W IE9500059 W IE 9500059W WO 9615136 A1 WO9615136 A1 WO 9615136A1
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Prior art keywords
substituted
complex according
carboxylate complex
carboxylate
unsubstituted
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PCT/IE1995/000059
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English (en)
Inventor
Michael Devereux
Martin Curran
Malachy Mccann
Michael Casey
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MAYNOOTH UNIVERSITY ENTERPRISE DEVELOPMENT Ltd
Technological University Dublin
Original Assignee
MAYNOOTH UNIVERSITY ENTERPRISE DEVELOPMENT Ltd
Technological University Dublin
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Priority to AU38803/95A priority Critical patent/AU3880395A/en
Priority to EP95938006A priority patent/EP0804444A1/fr
Publication of WO1996015136A1 publication Critical patent/WO1996015136A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • 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
  • novel complexes of the present invention are mono-, di- and polycarboxylate 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
  • 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.
  • a Mn(II) carboxylate complex or a binuclear or polynuclear derivative thereof in which the
  • carboxylate moiety is of the general formula Y[O m (CH 2 ) q COOH] p in which m is 0 or 1; q is ⁇ O; p is ⁇ 1; and Y is selected from the group comprising hydrogen,
  • substituted or unsubstituted lower (C 1-20 ) alkyl substituted or unsubstituted lower (C 2-20 ) alkenyl, substituted or unsubstituted lower (C 2-20 ) 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
  • alkynylene with the proviso that, when m is 0 and q is 0 or 1 and p is 1, Y is not hydrogen.
  • Y is substituted by halogen, hydroxyl, lower (C 1-20 ) alkoxy, nitro, a substituted or
  • Y is a carbocyclic ring system selected from the group comprising lower (C 3-20 ) 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
  • Y preferably C 6-12 aryl, optionally selected from phenyl, benzyl, naphthalenyl and anthracenyl, Y being
  • Y is naphthalenyl or
  • Y is (C 1-10 ) lower alkylene, optionally selected from dimethylene, trimethylene, tetramethylene, pentamethylene and hexamethylene; p is 2; and m and q are each 0.
  • Y is lower (C 2-20 ) alkenyl substituted by halogen, hydroxyl, lower (C 1-20 ) 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 - 10 ) alkenyl, optionally acrylyl, substituted by a heterocyclic ring system, most preferably
  • 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
  • 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 1-20 ) 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
  • Mn (II) L in which 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
  • 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 a Mn(II) carboxylate complex; and
  • 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, the reaction medium also containing an appropriate nitrogen donor ligand, to obtain the Mn(II)-carboxylate-nitrogen donor ligand complex of the invention.
  • a suitable reaction medium preferably selected from water or an ethanol:water mixture, more preferably a 4:1 (v:v) ethanol:water mixture, the reaction medium also containing an appropriate nitrogen donor ligand, to obtain the Mn(II)-carboxylate-nitrogen donor ligand complex of the invention.
  • 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
  • a simple manganese (II) salt eg. manganese (II) acetate tetrahydrate or manganese (II) chloride
  • odaH 2 octanedioic acid
  • salH 2 salicylic acid
  • ndaH 2 cis-5-norbornene-endo-2,3-dicarboxylic acid
  • bdoaH 2 benzene-1,2-dioxyacetic acid
  • bndaH 2
  • Example 1 Mn(oda).H 2 O (Complex 1) Mn(CH 3 CO 2 ) 2 ⁇ 4H 2 O (1.0 g, 4.08 mmol) and
  • 1,10-phenanthroline (1.13 g, 6.27 mmol) were refluxed together in an ethanol:water mixture (4:1) (50 ml) for 45 min.
  • the resulting yellow solution was allowed to cool to room temperature and on standing the product (2) formed as yellow crystals.
  • the crystals were filtered off, washed with ice-cold ethanol and then air-dried. Yield 51%. More of complex (2) was
  • Example 7 [Mn(nda)(H 2 O)] (Complex 7) To a solution of ndaH 2 (1.0 g, 5.49 mmol) and NaOH (0.48 g, 12.0 mmol) in distilled water (100 ml) was added MnCl 2 .4H 2 O (0.98 g, 4.96 mmol). The resulting colourless solution was stirred at room temperature for 3 hours. The solution was concentrated by slow
  • 1,10-phenanthroline (1.5 g). The resulting mixture was refluxed for 0.75 hours to give a yellow solution. Upon standing for several days, yellow crystals of the product (8) were deposited. The solid was filtered off, washed with a small portion of ice-cold ethanol and air-dried at ca 25°C. Yield 0.25g (65.4%). Calc: C, 63.73; H, 4.90; N, 8.50. Found: C, 64.56; H, 4.66; N, 8.40%.
  • IR CsI matrix: 3800, 3000, 1610, 1590, 1545, 1520, 1430, 1400, 1375, 1350, 1305, 1290, 1100, 860, 750, 735, 640 cm -1 .
  • Complex (8) readily dissolves in water and in warm ethanol.
  • 1,10-phenanthroline (0.65 g, 3.6 mmol). The mixture was refluxed for 2 hours and upon cooling the yellow product (10) precipitated. The solid was filtered off, washed with cool ethanol, and air-dried at ca 20°C.
  • Example 12 [Mn(bnda)(phen) 2 (H 2 O) 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 [Mn 2 (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.
  • each Mn(II) atom is at the centre of a distorted N 4 O 2 octahedron.
  • the structure of the dication [Mn 2 (oda)(phen) 4 (H 2 O) 2 ] 2+ is basically similar to that of the dianion in that each of the two symmetry related Mn(II) atoms has a distorted
  • 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.
  • Mn 2 (salH) 4 (H 2 O) 4 (Complex 3)
  • the complex comprises two associated and symmetry related pseudo seven-coordinate Mn(II) centres.
  • Each Mn is asymmetrically chelated by two salH- (HOC 6 H 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,
  • the complex comprises three independent Mn(II) atoms ⁇ Mn1, 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 Mn1.
  • Mn3 is in a general position, and is bonded to the second carboxylate oxygen atom from the sal 2- ligand which is coordinated to Mn1, 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 O + : oxygen donor ligand) are also coordinated to Mn3 , and the N 2 O 4 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
  • 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 O) 4 ] ( Complex 14 )
  • 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 H 2 O 2 (35% w/w, 10 ml, 114 mmol) was injected using a syringe.
  • the resulting mixture was stirred, and the evolved O 2 was measured volumetrically (ml) over a period of time (min).
  • the results are set out in Table 1 hereinbelow.
  • the complexes of the invention also catalyze the disproportionation of H 2 O 2 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
  • complexes of the present invention are suitable for use in surface cleaners and washing powders.

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Abstract

Nouveaux complexes de carboxylate de manganèse (II) utilisables comme catalyseurs de dismutation, et leurs procédés de préparation. On a mis au point des complexes de carboxylate de manganèse (II), ou leurs dérivés binucléaires ou polynucléaires, dans lesquels la fraction carboxylate est représentée par la formule générale Y[Om(CH2)qCOOH]p, dans laquelle m vaut 0 ou 1; q est ≥ 0; p est ≥ 1; et Y, qui est éventuellement substitué, est choisi parmi alkyle inférieur, alcényle inférieur, alcynyle inférieur, un système à noyau carbocyclique, un hydrocarbure aromatique ou un système à noyau hétérocyclique, et, lorsque p vaut 2, Y, lui aussi éventuellement substitué, est en outre choisi parmi alkylène inférieur, alcénylène inférieur ou alcynylène inférieur, à condition que si m vaut 0, q vaut 0 ou 1 et p vaut 1, Y ne représente pas hydrogène.
PCT/IE1995/000059 1994-11-14 1995-11-14 Nouveaux complexes de carboxylate de manganese (ii), leurs procedes de preparation et leur utilisation comme catalyseurs de dismutation Ceased WO1996015136A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU38803/95A AU3880395A (en) 1994-11-14 1995-11-14 Novel mn(ii) carboxylate complexes, processes for their preparation and their use as disproportionation catalysts
EP95938006A EP0804444A1 (fr) 1994-11-14 1995-11-14 Nouveaux complexes de carboxylate de manganese (ii), leurs procedes de preparation et leur utilisation comme catalyseurs de dismutation

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IE940892 1994-11-14
IES940892 1994-11-14

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WO1996015136A1 true WO1996015136A1 (fr) 1996-05-23

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5969171A (en) * 1997-07-01 1999-10-19 Clariant Gmbh Metal complexes as bleach activators
US5998645A (en) * 1997-05-07 1999-12-07 Clariant Gmbh Bleaching-active metal complexes
US6139769A (en) * 1997-04-05 2000-10-31 Clariant Gmbh Bleaching-active metal complexes
CN104447819A (zh) * 2014-11-12 2015-03-25 东北师范大学 双萘基二乙酸的手性锌配合物及其制备方法
US20160168515A1 (en) * 2013-07-24 2016-06-16 Michael B. Abrams Manganese carboxylates for peroxygen activation
CN106905377A (zh) * 2017-02-27 2017-06-30 衡阳师范学院 一种茂基双核椅状钴氮配合物及其制备方法和应用
RU2737435C1 (ru) * 2020-04-30 2020-11-30 Федеральное государственное бюджетное учреждение науки Институт органического синтеза им. И.Я. Постовского Уральского отделения Российской академии наук Смешанные металлокомплексы на основе 5-(4-метилфенил)-2,2'-бипиридина и (тетрафтор)салициловых кислот, обладающие антибактериальной и фунгистатической активностью

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US5025101A (en) * 1990-06-21 1991-06-18 Exxon Research & Engineering Company Novel tetranuclear manganese complexes
US5256779A (en) * 1992-06-18 1993-10-26 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
US5280117A (en) * 1992-09-09 1994-01-18 Lever Brothers Company, A Division Of Conopco, Inc. Process for the preparation of manganese bleach catalyst

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US5025101A (en) * 1990-06-21 1991-06-18 Exxon Research & Engineering Company Novel tetranuclear manganese complexes
US5256779A (en) * 1992-06-18 1993-10-26 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
US5280117A (en) * 1992-09-09 1994-01-18 Lever Brothers Company, A Division Of Conopco, Inc. Process for the preparation of manganese bleach catalyst

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Title
CASEY M T ET AL: "Synthesis and structure of the MnII,II complex salt [Mn2(.eta.1.eta.1.mu.2-oda)(phen)4(H2O)2][Mn2(.eta.1.eta.1.mu.2-oda)( phen)4(.eta.1-oda)2].4H2O (odaH2 = octanedioic acid): a catalyst for H2O2 disproportionation", J. CHEM. SOC., CHEM. COMMUN. (JCCCAT,00224936);94; (22); PP.2643-5, - 21 November 1994 (1994-11-21), ST. PATRICK'S COLLEGE;CHEMISTRY DEPARTMENT; KILDARE; IRE. (IE) *
DEVEREUX M ET AL: "Binuclear and polymeric manganese(II) salicylate complexes: synthesis, crystal structure and catalytic activity of [Mn2(Hsal)4(H2O)4] and [{Mn2(sal)2(Hsal)(H2O)(H3O)(py)4.cntdot.2py}n] (H2sal = salicylic acid, py = pyridine)", J. CHEM. SOC., DALTON TRANS. (JCDTBI,03009246);95; (5); PP.771-6, DUBLIN INSTITUTE TECHNOLOGY;DUBLIN; ISRAEL (IL) *
DEVEREUX M ET AL: "Synthesis and catalase activity of manganese(II) complexes of cis-5-norbornene-endo-2,3-dicarboxylic acid (ndaH2): x-ray crystal structure of [Mn(.eta.1.eta.1-nda)(phen)2]. EtOH.H2O (phen = 1,10-phenanthroline)", POLYHEDRON (PLYHDE,02775387);95; VOL.14 (15/16); PP.2247-53, DUBLIN INST. OF TECHNOLOGY;DUBLIN; IRE. (IE), XP000563969 *
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US6139769A (en) * 1997-04-05 2000-10-31 Clariant Gmbh Bleaching-active metal complexes
US6602441B1 (en) 1997-04-05 2003-08-05 Clariant Gmbh Bleaching-active metal complexes
US5998645A (en) * 1997-05-07 1999-12-07 Clariant Gmbh Bleaching-active metal complexes
US5969171A (en) * 1997-07-01 1999-10-19 Clariant Gmbh Metal complexes as bleach activators
US20160168515A1 (en) * 2013-07-24 2016-06-16 Michael B. Abrams Manganese carboxylates for peroxygen activation
EP3024918A4 (fr) * 2013-07-24 2016-12-14 Arkema Inc Carboxylate de manganèse pour l'activation des peroxygènes
CN104447819A (zh) * 2014-11-12 2015-03-25 东北师范大学 双萘基二乙酸的手性锌配合物及其制备方法
CN106905377A (zh) * 2017-02-27 2017-06-30 衡阳师范学院 一种茂基双核椅状钴氮配合物及其制备方法和应用
CN106905377B (zh) * 2017-02-27 2019-02-19 衡阳师范学院 一种茂基双核椅状钴氮配合物及其制备方法和应用
RU2737435C1 (ru) * 2020-04-30 2020-11-30 Федеральное государственное бюджетное учреждение науки Институт органического синтеза им. И.Я. Постовского Уральского отделения Российской академии наук Смешанные металлокомплексы на основе 5-(4-метилфенил)-2,2'-бипиридина и (тетрафтор)салициловых кислот, обладающие антибактериальной и фунгистатической активностью

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