EP0804444A1 - Novel mn(ii) carboxylate complexes, processes for their preparation and their use as disproportionation catalysts - Google Patents
Novel mn(ii) carboxylate complexes, processes for their preparation and their use as disproportionation catalystsInfo
- Publication number
- EP0804444A1 EP0804444A1 EP95938006A EP95938006A EP0804444A1 EP 0804444 A1 EP0804444 A1 EP 0804444A1 EP 95938006 A EP95938006 A EP 95938006A EP 95938006 A EP95938006 A EP 95938006A EP 0804444 A1 EP0804444 A1 EP 0804444A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- substituted
- complex according
- carboxylate complex
- carboxylate
- unsubstituted
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
- 150000007942 carboxylates Chemical class 0.000 title claims abstract description 23
- 238000007323 disproportionation reaction Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 Mn(II) carboxylate Chemical class 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 9
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004450 alkenylene group Chemical group 0.000 claims abstract description 3
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 3
- 125000004419 alkynylene group Chemical group 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 100
- 229910001868 water Inorganic materials 0.000 claims description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 80
- 239000003446 ligand Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 30
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 101100451327 Pseudomonas furukawaii salH gene Proteins 0.000 claims description 16
- 125000003367 polycyclic group Chemical group 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical group 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 9
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 8
- 239000012429 reaction media Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 235000007586 terpenes Nutrition 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 125000002140 imidazol-4-yl group Chemical group [H]N1C([H])=NC([*])=C1[H] 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims 6
- 150000001735 carboxylic acids Chemical class 0.000 claims 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- 150000003335 secondary amines Chemical class 0.000 claims 1
- 150000003512 tertiary amines Chemical class 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 33
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 229960005137 succinic acid Drugs 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 2
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 2
- 229960001860 salicylate Drugs 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- LOIYMIARKYCTBW-UHFFFAOYSA-N trans-urocanic acid Natural products OC(=O)C=CC1=CNC=N1 LOIYMIARKYCTBW-UHFFFAOYSA-N 0.000 description 2
- FNZBSNUICNVAAM-UHFFFAOYSA-N trimethyl-[methyl-[methyl-(methyl-phenyl-trimethylsilyloxysilyl)oxy-phenylsilyl]oxy-phenylsilyl]oxysilane Chemical compound C=1C=CC=CC=1[Si](C)(O[Si](C)(C)C)O[Si](C)(C=1C=CC=CC=1)O[Si](C)(O[Si](C)(C)C)C1=CC=CC=C1 FNZBSNUICNVAAM-UHFFFAOYSA-N 0.000 description 2
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- DGOBMKYRQHEFGQ-UHFFFAOYSA-L acid green 5 Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 DGOBMKYRQHEFGQ-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000004973 alkali metal peroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 238000012866 crystallographic experiment Methods 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical group O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000020095 red wine Nutrition 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
Classifications
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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
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- 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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DE19714122A1 (en) | 1997-04-05 | 1998-10-08 | Clariant Gmbh | Bleach-active metal complexes |
DE19719397A1 (en) * | 1997-05-07 | 1998-11-12 | Clariant Gmbh | Bleach-active metal complexes |
DE19728021A1 (en) * | 1997-07-01 | 1999-01-07 | Clariant Gmbh | Metal complexes as bleach activators |
ES2746314T3 (en) * | 2013-07-24 | 2020-03-05 | Arkema Inc | Manganese carboxylates for peroxygen activation |
CN104447819B (en) * | 2014-11-12 | 2016-10-05 | 东北师范大学 | Chiral zinc nitrogen complexes of double naphthyl oxalic acid and preparation method thereof |
CN106905377B (en) * | 2017-02-27 | 2019-02-19 | 衡阳师范学院 | A kind of cyclopentadienyl double-core chair shape cobalt nitrogen complex and its preparation method and application |
RU2737435C1 (en) * | 2020-04-30 | 2020-11-30 | Федеральное государственное бюджетное учреждение науки Институт органического синтеза им. И.Я. Постовского Уральского отделения Российской академии наук | Mixed metal complexes based on 5-(4-methylphenyl)-2,2'-bipyridine and (tetrafluor) salicylic acids, having antibacterial and fungistatic activity |
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