CN101631775A - 金属络合物 - Google Patents
金属络合物 Download PDFInfo
- Publication number
- CN101631775A CN101631775A CN200880007673A CN200880007673A CN101631775A CN 101631775 A CN101631775 A CN 101631775A CN 200880007673 A CN200880007673 A CN 200880007673A CN 200880007673 A CN200880007673 A CN 200880007673A CN 101631775 A CN101631775 A CN 101631775A
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- Prior art keywords
- metal complex
- formula
- metal
- group
- compound
- Prior art date
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- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 168
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 48
- 150000003624 transition metals Chemical class 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 125000004429 atom Chemical group 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000006615 aromatic heterocyclic group Chemical group 0.000 abstract description 3
- 125000001424 substituent group Chemical group 0.000 abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 64
- -1 metal complex compound Chemical class 0.000 description 59
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 49
- 239000000243 solution Substances 0.000 description 45
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 40
- 238000003756 stirring Methods 0.000 description 29
- 230000002194 synthesizing effect Effects 0.000 description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 24
- 239000012299 nitrogen atmosphere Substances 0.000 description 24
- 238000001914 filtration Methods 0.000 description 22
- 239000007787 solid Substances 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 20
- 239000002253 acid Substances 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 238000001035 drying Methods 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 15
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- 238000004140 cleaning Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 238000004062 sedimentation Methods 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 125000002541 furyl group Chemical group 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 125000004076 pyridyl group Chemical group 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 125000000335 thiazolyl group Chemical group 0.000 description 6
- 125000001544 thienyl group Chemical group 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000006479 redox reaction Methods 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 150000002240 furans Chemical class 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 229910052762 osmium Inorganic materials 0.000 description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 125000003373 pyrazinyl group Chemical group 0.000 description 4
- 125000002098 pyridazinyl group Chemical group 0.000 description 4
- 229910052702 rhenium Inorganic materials 0.000 description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 4
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 4
- 239000001433 sodium tartrate Substances 0.000 description 4
- 229960002167 sodium tartrate Drugs 0.000 description 4
- 235000011004 sodium tartrates Nutrition 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 229940113088 dimethylacetamide Drugs 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 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 3
- 239000012046 mixed solvent Substances 0.000 description 3
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003233 pyrroles Chemical class 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KXCSFSWUZFEBQT-UHFFFAOYSA-L O.O.O.O.O.O.O.O.[Mn](=O)(Cl)Cl Chemical compound O.O.O.O.O.O.O.O.[Mn](=O)(Cl)Cl KXCSFSWUZFEBQT-UHFFFAOYSA-L 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 241000545067 Venus Species 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
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Images
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
- C07F15/06—Cobalt compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
-
- 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
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Abstract
本发明提供一种以下式(1)表示的金属络合物(式中,R1~R6各自独立地表示氢原子或取代基,Y1及Y2各自独立地表示如式(II)所示(Rα是氢原子或碳数为1~4的烃基)。P1及P2是与Y1和Y1的邻位或与Y2和Y2的邻位的2个碳原子成为一体形成杂环所必需的原子组,M表示过渡金属元素或典型金属元素。m表示1或2,X是平衡离子或中性分子,n是处于络合物中的X的个数,表示0以上的整数,Q1及Q2各自独立地表示芳香族杂环基)。
Description
技术领域
本发明涉及一种金属络合物,更具体来说,涉及一种作为催化剂来说有用的金属络合物。
背景技术
金属络合物作为氧加成反应、氧化偶联反应、脱氢反应、加氢反应、氧化物分解反应、电极反应等伴随着电子移动的氧化还原反应中的催化剂发挥作用,被用于有机化合物或高分子化合物的制造中。另外,最近被作为有机EL材料的磷光发光络合物使用。此外,还用于添加剂、改性剂、电池、传感器的材料等各种用途中。
特别是作为氧化还原反应催化剂,已知希夫式碱型金属络合物具有高活性、高选择性的催化能力。例如,在Org.Biomol.Chem.,2005,3,2126中,在催化剂中使用光学活性的希夫式碱型络合物,将苯乙烯的双键氧化,引起不对称环丙烷化反应,进行良好的不对称反应。另外,在Inorg.Chem.,2001,40,1329中,使用希夫式碱型金属络合物,进行利用氧的电解还原的水的生成。
但是,Org.Biomol.Chem.,2005,32126中所公布的金属络合物在将其作为催化剂使用的情况下,在加热下催化剂变得不稳定,活性有可能降低。此外,该催化剂在强酸的存在下,也有可能发生不稳定化,是应用范围受到了限定的催化剂。如此所述,以往所公布的金属络合物有可能因反应条件而分解。
发明内容
根据本发明,可以提供一种稳定性优异、对于氧化还原反应催化等来说有用的金属络合物。
根据本发明,提供以下的途径。
(1)一种以下式(1)表示的金属络合物。
(式中,R1~R6各自独立地表示氢原子或取代基,R1与R2、R2与R3、R4与R5及/或R5与R6也可以相互结合而形成环。Y1及Y2各自独立地表示
(Rα是氢原子或碳数为1~4的烃基。)。P1是为了与Y1和Y1的邻位的2个碳原子一体化地形成杂环而必需的原子组,P2是为了与Y2和Y2的邻位的2个碳原子一体化地形成杂环而必需的原子组,P1与P2也可以相互结合而形成环。M表示周期表中记载的过渡金属元素或典型金属元素。m表示1或2,在m为2的情况下,2个M既可以相同也可以不同。X是平衡离子或中性分子,n是处于络合物中的X的个数,表示0以上的整数,在有多个X的情况下,它们既可以相同也可以不同。Q1及Q2各自独立地表示芳香族杂环基。)
(2)一种以下式(2)表示的金属络合物。
(式中,R7~R18各自独立地表示氢原子或取代基,R7与R10、R7与R8、R8与R9、R9与R13、R10与R11、R12与R12、R12与R16、R13与R14、R14与R15、R16与R17、R17与R18的各个组的2个取代基也可以相互连结而形成环。
M表示周期表(IUPAC2001年)中记载的过渡金属元素或典型金属元素。m表示1或2的整数,在m为2的情况下,2个M既可以相同也可以不同。X是平衡离子或中性分子,n是处于络合物中的X的个数,表示0以上的整数,在有多个X的情况下,它们既可以相同也可以不同。Q3及Q4各自独立地表示芳香族杂环基。)
(3)根据上述(1)或(2)所述的金属络合物,在上述式(1)及(2)中,m为2,M是周期表(IUPAC2001年)中记载的第3族~第9族的过渡金属元素。
(4)根据上述(1)或(2)所述的金属络合物,在上述式(1)及(2)中,m为1。
(5)一种具有以上述式(1)或(2)表示的金属络合物的残基的聚合物。
(6)根据上述(5)所述的聚合物,具有上式(1)或(2)所示的金属络合物的残基作为重复单元。
(7)一种使用(1)~(6)中任一项所述的金属络合物及/或聚合物制成的催化剂。
本发明的上述以及其他的特征及优点可以适当地参照附图,根据下述的记载进一步明确。
附图说明
图1表示金属络合物(A)的IR吸收光谱。
图2表示金属络合物(M)的IR吸收光谱。
图3表示金属络合物(N)的IR吸收光谱。
图4表示金属络合物(W)的IR吸收光谱。
图5表示实施例29及比较例7的过氧化氢分解试验的结果。
具体实施方式
对作为本发明的第一实施方式的以上述式(1)表示的金属络合物进行说明。
该金属络合物是作为过渡金属原子元素或典型金属元素的金属原子M利用具有4个杂原子和2个氧原子的配体形成络合物的物质。另外,连结氧原子与金属原子的键是配位键或离子键,在有2个金属原子的情况下,也可以在金属原子间进行交联配位。这里,所谓“过渡金属”与“化学大辞典”(大木道则等编、平成17年7月1日发行、东京化学同人)1283页中作为“过渡元素”记载的内容同义,是指具有不完全的d或f亚层的元素。而且,本发明中的所谓过渡金属原子M既可以无电荷,也可以是带电的离子。另外,对于典型金属原子M也是相同的,既可以无电荷,也可以是带电的离子。
这里,如果对过渡金属M进行具体地例示,则可以举出钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、钇、锆、铌、钼、钌、铑、钯、银、镉、铪、钽、钨、铼、锇、铱、铂、金、汞。
另外,如果对典型金属进行具体地例示,则可以举出铝、镓、锗、铟、锡、锑、铊、铅、铋。
以通式(1)表示的金属络合物优选为以通式(2)表示的化合物。
上述式(1)及(2)中所述的M在m为2的情况下,优选为选自上述周期表中记载的第3族~第9族的过渡金属原子中的金属原子,2个M既可以相互不同,也可以相同。
上述的m为2时的第3~9族的过渡金属原子M优选为钪、钛、钒、铬、锰、铁、钴、钇、锆、铌、钼、钌、铑、铪、钽、钨、铼、锇、铱,更优选为钛、钒、铬、锰、铁、钴、锆、铌、钼、钌、铑,特别优选为第四周期的过渡金属,具体来说,为钛、钒、铬、锰、铁、钴。本发明中如前所述,也可以是这些过渡金属的离子。
上述式(1)及(2)中所述的M在m为1的情况下,表示选自上述的周期表中记载的过渡金属原子及典型金属原子中的1个,优选为铝、钛、钒、铬、锰、铁、钴、镍、铜、锌、镓、锗、锆、铌、钼、钌、铑、钯、银、镉、铟、锡、锑、钽、钨、铼、锇、铱、铂或金,更优选为铝、钛、钒、铬、锰、铁、钴、镍、铜、锌、镓、钼、钌、铑、钯、银、钨、铼、锇、铱、铂或金,特别优选为第四周期的过渡金属,具体来说,为钛、钒、铬、锰、铁、钴、镍、铜、锌。本发明中M如前所述,也可以是过渡金属及典型金属的离子。
下面,对以上述式(1)表示的金属络合物的配体进行说明。上述式(1)的R1~R6各自独立地表示氢原子或取代基。
这里,如果对取代基进行具体地记述,则可以例示出氟基、氯基、溴基、碘基等卤素基,羟基,羧基,巯基,磺酸基,硝基,磷酸基,具有碳数为1~4的烷基的甲硅烷基,甲基、乙基、丙基、异丙基、环丙基、丁基、异丁基、叔丁基、戊基、环戊基、己基、环己基、降冰片基、壬基、环壬基、癸基、3,7-二甲基辛基、金刚烷基、十二烷基、环十二烷基、十五烷基、十八烷基、二十烷基等总碳数为1~50左右的直链、支链或环状的饱和烃基,甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、环己氧基、降冰片氧基、癸氧基、十二烷氧基等总碳数为1~50左右的直链、支链或环状的烷氧基,苯基、4-甲基苯基、1-萘基、2-萘基、9-蒽基等总碳数为6~60左右的芳香族基等。
作为R1~R6,优选氟基、氯基、溴基、碘基等卤素基,巯基,羟基,羧基,以甲基、乙基、丙基、异丙基、丁基、戊基、叔丁基、环己基、降冰片基、金刚烷基来例示的总碳数为1~20左右的烃基、以甲氧基、乙氧基、丙氧基、丁氧基、戊氧基来例示的总碳数为1~10左右的直链、支链的烷氧基,苯基、1-萘基、2-萘基、9-蒽基等总碳数为6~30左右的芳香族基及氢原子。
更优选为氯基、溴基、羟基、羧基、甲基、乙基、叔丁基、环己基、降冰片基、金刚烷基、甲氧基、乙氧基、苯基及氢原子。
R1与R2、R2与R3、R4与R5、R5与R6的各个组的2个取代基可以相互连结而形成环。
这里所说的环可以举出环己烷环、苯环、萘环、蒽环、苊环等烃环,呋喃环、噻吩环等芳香族杂环。
而且,利用2个取代基的组合来连结而形成的环也可以在该环上还具有取代基,作为这些取代基,可以举出与前面所例示出的取代基同等的基团。
Y1及Y2各自独立地表示
(Rα是氢原子或碳数为1~8、优选为1~4的烃基。)。以Rα表示的一价的烃基与作为上述的取代基例示的基团相同。P1及P2各自独立地表示为了与Y1及Y2的各自的邻位的2个碳原子一体化地形成杂环而必需的原子组(以下也称作“P1及P2骨架”。)。而且,在该邻位的2个碳原子中,不包含Rα中所含的碳原子。作为杂环的具体例,可以举出吡啶、吡嗪、嘧啶、吡咯、N-烷基吡咯、呋喃、噻吩、噻唑、咪唑、噁唑、苯并咪唑、苯并呋喃、苯并噻吩、异喹啉、喹唑啉,优选为吡啶、吡嗪、嘧啶、吡咯、呋喃、噻吩、N-烷基吡咯,更优选为吡啶、吡咯、呋喃、噻吩。
另外,也可以是P1与P2骨架相互结合而形成新的环,优选具有下述式(1-a)~(1-i)的结构的环,更优选为式(1-a)~(1-d)。
这里,R表示氢原子或碳数以1~30表示的烃基。
而且,P1与P2骨架也可以具有取代基,作为这些取代基,可以举出与适用于前面所例示的R1~R6中的取代基同等的基团。
另外,作为取代基的Q1及Q2表示芳香族杂环基。本发明中所说的芳香族杂环基具体来说是吡啶基、吡嗪基、嘧啶基、哒嗪基、吡咯基、呋喃基、噻吩基、噻唑基、咪唑基、噁唑基、三唑基、吲哚基、苯并咪唑基、苯并呋喃基、苯并噻吩基、喹啉基、异喹啉基、噌啉基、酞嗪基、喹唑啉基、喹喔啉基、benzodiazinyl等。优选吡啶基、吡嗪基、哒嗪基、吡咯基、呋喃基、噻吩基、噻唑基、吲哚基、苯并咪唑基,更优选吡啶基、吡咯基、呋喃基、噻吩基、噻唑基。
另外,也可以在这些环上还具有取代基,可以举出与前面所例示的R1~R6同等的基团。
以上述式(1)表示的金属络合物优选具有从以上述P1及P2、Y1及Y2的具体例表示的基团、以上述Q1及Q2的具体例表示的基团中组合而产生的配体结构的化合物。
此外,作为本发明的金属络合物,优选以上述式(2)表示的金属络合物。作为该配体,如前所述,作为配位原子具有至少2个氮原子和2个氧原子。该环也可以具有取代基,上述式(2)的R7~P18各自独立地表示氢原子或取代基。
这里所说的取代基具有与上述式(1)中所述的R1~P6相同的取代基。
Q3及Q4表示芳香族杂环基。所谓芳香族杂环基,作为具体例,可以举出吡啶基、吡嗪基、嘧啶基、哒嗪基、吡咯基、呋喃基、噻吩基、噻唑基、咪唑基、噁唑啉基、三唑基、吲哚基、苯并咪唑基、苯并呋喃基、苯并噻吩基、喹啉基、异喹啉基、噌啉基、酞嗪基、喹唑啉基、喹喔啉基、benzodiazinyl,优选吡啶基、吡嗪基、哒嗪基、吡咯基、呋喃基、噻吩基、噻唑基、吲哚基、苯并咪唑基,更优选吡啶基、吡咯基、呋喃基、噻吩基、噻唑基。虽然在这些环的任何部位结合都可以,然而优选在杂元素的邻位或间位结合。
另外,这些芳香族杂环基Q3及Q4也可以还具有取代基,作为这些取代基,可以举出与适用于上述式(1)中所例示的R1~P6中的取代基同等的基团。
以上述式(2)表示的金属络合物优选具有以上述Q1及Q2的具体例表示的基团中组合而产生的配体结构的化合物。具体来说,更优选具有以下所示的配体骨架结构(I)~(XII)的化合物。
上述骨架结构(III)、(V)、(VI)、(VIII)中记载的R表示氢原子或碳数为1~30的烃基。
上述结构(I)~(XII)的电荷省略。
上述式(1)及(2)的X是中性分子,或将金属络合物变为电中性的平衡离子。该所谓中性分子可以举出发生溶剂化而形成溶剂化盐的分子、上述式(1)~(2)的环状配体以外的配体。具体来说,如果要例示该中性分子,则为水、甲醇、乙醇、正丙醇、异丙醇、2-甲氧基乙醇、1,1-二乙基乙醇、乙二醇、N,N’-二甲替甲酰胺、N,N’-二甲替乙酰胺、N-甲基-2-吡咯烷酮、二甲亚砜、丙酮、氯仿、乙腈、苄腈、三乙胺、吡啶、吡嗪、二氮杂-双环[2,2,2]辛烷、4,4’-联吡啶、四氢呋喃、二乙醚、二甲氧基乙烷、甲乙醚、1,4-二噁烷。优选为水、甲醇、乙醇、异丙醇、乙二醇、N,N’-二甲替甲酰胺、N,N’-二甲替乙酰胺、N-甲基-2-吡咯烷酮、氯仿、乙腈、苄腈、三乙胺、吡啶、吡嗪、二氮杂-双环[2,2,2]辛烷、4,4’-联吡啶、四氢呋喃、二甲氧基乙烷、1,4-二噁烷。
另外,在X为离子的情况下,通常来说,由于过渡金属原子及典型金属原子具有正的电荷,因此选择将其变为电中性的阴离子,为氟离子、氯离子、溴离子、碘离子、硫化物离子、氧化物离子、氢氧化物离子、氢化物离子、亚硫酸离子、磷酸离子、氰化物离子、乙酸离子、碳酸离子、硫酸离子、硝酸离子、碳酸氢离子、三氟乙酸离子、2-乙基己酸离子、硫氰化物离子、三氟甲磺酸离子、乙酰乙酸酯、四氟硼酸离子、六氟磷酸离子、四苯基硼酸离子。优选为氯化物离子、溴化物离子、碘化物离子、氧化物离子、氢氧化物离子、氢化物离子、磷酸离子、氰化物离子、乙酸离子、碳酸离子、硫酸离子、硝酸离子、2-乙基己酸离子、乙酰乙酸酯、四苯基硼酸离子。
另外,在存在多个X的情况下,它们既可以相同,也可以不同,也可以是中性分子与离子共存的形态。
以上述式(2)表示的金属络合物具体来说优选将上述所述的配体骨架结构(I)~(XII)及上述所述的M以及X的具体例组合而成的化合物,特别优选的金属络合物是将上述所述的配体骨架结构(I)~(IV)及第四周期的过渡金属原子M以及乙酸离子、氯化物离子、硝酸离子、2-乙基己酸离子组合而产生的化合物。
所谓具有以上述式(1)或(2)表示的金属络合物的残基的聚合物,是指具有由将以上述式(1)或(2)表示的金属络合物的氢原子的一部分或全部(通常来说为1个)去除而形成的原子团构成的基团的聚合物,作为此时所用的聚合物,没有特别限制,然而可以例示出导电性高分子、树状物(dendrimer)、天然高分子、固体高分子电解质、聚乙烯、聚乙二醇、聚丙烯等。其中特别优选导电性高分子、固体高分子电解质。所谓导电性高分子是显示出金属的或半金属的导电性的高分子物质的总称(岩波理化学辞典第5版:1988年发行)。作为导电性高分子,可以举出如《导电性聚合物》(吉村进一著、共立出版)或《导电性高分子的最新应用技术》(小林征男主编、CMC出版)中所述的聚乙炔及其衍生物、聚对亚苯及其衍生物、聚对苯乙炔及其衍生物、聚苯胺及其衍生物、聚噻吩及其衍生物、聚吡咯及其衍生物、聚芴及其衍生物、聚芴及其衍生物、聚咔唑及其衍生物、聚吲哚及其衍生物、以及上述导电性高分子的共聚物等。
作为固体高分子电解质,可以举出全氟磺酸、聚醚醚酮、聚酰亚胺、聚苯撑、聚芳撑、将聚芳醚砜磺化了的高分子等。
所谓作为重复单元具有以上述式(1)或(2)表示的金属络合物的残基的聚合物,是指作为重复单元具有由将以上述式(1)或(2)表示的金属络合物的氢原子的一部分或全部(通常来说为2个)去除而形成的原子团构成的基团的聚合物,例如为通过将含有大环状配体的双官能性单体聚合而生成的聚合物。
下面,对以上述式(1)及(2)表示的金属络合物的合成法进行说明。
以上述式(1)及(2)表示的金属络合物可以通过首先以有机化学方式合成配体,将其与赋予金属原子M的反应剂(以下称作“金属赋予剂”)在反应溶剂中混合而得到。这里,金属赋予剂是由上述所述的金属原子M与平衡离子X的组合构成的金属盐,作为金属原子M的优选的具体的例示,可以举出锰、铁、钴、镍、铜,作为平衡离子X的优选的具体的例示,可以举出乙酸离子、氯化物离子、硝酸离子、2-乙基己酸离子,优选由这些金属原子M与平衡离子X的组合构成的金属盐。
配体的合成可以如非专利文献Tetrahedron.,1999,55,8377.中所述那样,通过在进行了有机金属反应剂向芳香族杂环化合物上的加成反应及氧化后,进行卤化反应,继而进行使用了过渡金属催化剂的交叉偶联反应来合成。
另外,也可以通过进行使用了被卤化的芳香族杂环化合物的多阶段的交叉偶联反应来合成。
如前所述,本发明的金属络合物可以通过将配体及金属赋予剂在适当的反应溶剂的存在下混合而得到。具体来说,作为反应溶剂,可以举出水、乙酸、草酸、氨水、甲醇、乙醇、正丙醇、异丙醇、2-甲氧基乙醇、1-丁醇、1,1-二甲基乙醇、乙二醇、二乙醚、1,2-二甲氧基乙烷、甲乙醚、1,4-二噁烷、四氢呋喃、苯、甲苯、二甲苯、均三甲苯、均四甲苯、十氢化萘、二氯甲烷、氯仿、四氯化碳、氯苯、1,2-二氯苯、N,N’-二甲替甲酰胺、N,N’-二甲替乙酰胺、N-甲基-2-吡咯烷酮、二甲基亚砜、乙酮、乙腈、苄腈、三乙胺、吡啶,也可以使用将它们混合2种以上而形成的反应溶剂,然而优选能够溶解配体及金属赋予剂的溶剂。作为反应温度通常来说为-10~200℃,优选为0~150℃,特别优选为0~100℃,另外,作为反应时间通常来说以1分钟~1周,优选以5分钟~24小时,特别优选以1小时~12小时来实施。而且,对于反应温度及反应时间,也可以根据配体及金属赋予剂的种类适当地最佳化。
作为从反应后的反应溶液中离析提纯所生成的金属络合物的途径,可以从公知的重结晶法、再沉淀法或色谱法中适当地选择使用最佳的途径,也可以将这些途径组合。
而且,根据上述反应溶剂的种类,会有所生成的金属络合物析出的情况,通过将所析出的金属络合物利用过滤等固液分离途径来分离,根据需要进行清洗操作或干燥操作,也可以将金属络合物离析提纯。
以上述式(1)及(2)表示的金属络合物由于其基本骨架为芳香族,所以都具有高度的耐热性和耐酸性,即使在高温下或强酸的存在下也可以稳定地维持络合物结构,因此可以期待对2个金属点位的催化作用。
该金属络合物作为用途来说尤其适用于氧化还原催化等中,具体来说,可以举出过氧化氢的分解催化、芳香族化合物的氧化聚合催化、废气·废水净化用催化、染料敏化太阳能电池的氧化还原催化层、二氧化碳还原催化、改性氢制造用催化、氧传感器等用途。另外可以认为,利用共轭拓宽,还可以作为有机EL发光材料、有机晶体管以及染料敏化太阳能电池等有机半导体材料使用。
本发明的金属络合物稳定性(例如耐热性、耐酸性等)优异,对于氧化还原反应催化等十分有用。所以,该金属络合物即使在高温下或强酸的存在下,也可以抑制催化活性的降低,能够成为应用用途宽的催化剂,因此在工业上十分有用。
下面,基于实施例对本发明进行更具体的说明,然而本发明并不限定于它们。而且,下述例子中,Me表示甲基,Et表示乙基,Ac表示乙酰基。
实施例
[实施例1](金属络合物(A)的合成)
通过依照以下的反应式,将含有配体和乙酸钴四水合物的2-甲氧基乙醇混合·反应,而合成了金属络合物(A)。成为络合物的原料的下述配体是基于Tetrahedron.,1999,55,8377合成的。
首先,在氮气气氛下,将含有1.388g的配体和1.245g的乙酸钴四水合物的2-甲氧基乙醇200ml溶液加入500ml的梨形烧瓶中,在加热为60℃的同时搅拌2小时,生成了深棕色固体。通过将该固体过滤,继而用2-甲氧基乙醇20ml清洗、干燥,得到了金属络合物(A)(产量1.532g)。将所得的金属络合物(A)的红外线(IR)吸收光谱表示于图1中。
元素分析值(%):计算值(作为C49H50Co2N4O8);C,62.56;H,5.36;N,5.96;Co,12.53.实测值:C,62.12;H,5.07;N,6.03;Co,12.74。ESI-MS[M-OAc]+:805.0
[实施例2](金属络合物(B)的合成)
通过依照以下的反应式,将含有配体和乙酸钴四水合物的乙醇混合·反应,而合成了金属络合物(B)。成为络合物的原料的下述配体是基于Tetrahedron.,1999,55,8377合成的。
首先,在氮气气氛下,将含有0.315g的该配体和0.124g的乙酸钴四水合物的50ml乙醇溶液加入100ml的梨形烧瓶中,在80℃下搅拌1小时。通过在将所生成的深棕色沉淀过滤而用乙醇清洗后,进行真空干燥,得到了金属络合物(B)(产量0.270g)。
元素分析值(%):计算值(作为C42H40CoN4O4);C,69.70;H,5.57;N,7.74;实测值:C,70.01;H,5.80;N,7.56。ESI-MS[M·]+:687.1
[实施例3](金属络合物(C)的合成)
通过依照以下的反应式,将含有配体的乙醇溶液和含有乙酸铁的甲醇溶液混合·反应,而合成了金属络合物(C)。成为络合物的原料的下述配体是基于Tetrahedron.,1999,55,8377合成的。
首先,在氮气气氛下,将含有0.126g的配体的乙醇10ml溶液和含有0.078g的乙酸铁的甲醇5ml溶液加入50ml的梨形烧瓶中,在加热为80℃的同时搅拌3小时后,析出了深棕色固体。通过将该固体过滤,继而用甲醇清洗、干燥,得到了金属络合物(C)(产量0.075g)。元素分析值(%):计算值(作为C48H50Fe2N4O8);C,62.49;H,5.46;N,6.07.实测值:C,59.53;H,5.29;N,5.70。
[实施例4](金属络合物(D)的合成)
通过依照以下的反应式,将含有配体的氯仿溶液和含有氯化锰四水合物的乙醇溶液混合·反应,而合成了金属络合物(D)。成为络合物的原料的下述配体是基于Tetrahedron.,1999,55,8377合成的。
首先,在氮气气氛下,将含有0.126g的配体的氯仿2ml溶液和含有0.089g的氯化锰四水合物的乙醇6ml溶液加入25ml的梨形烧瓶中,在加热为80℃的同时搅拌3小时后,析出了黄色固体。通过将该固体过滤,继而用氯仿和乙醇清洗、干燥,得到了金属络合物(D)(产量0.092g)。元素分析值(%):计算值(作为C42H40Mn2N4O4);C,59.66;H,4.77;N,6.63;实测值:C,58.26;H,4.58;N,6.33。FD-MS[M·]+:808.0
[实施例5](金属络合物(E)的合成)
通过依照以下的反应式,将含有配体的乙醇溶液和含有乙酸锰四水合物的甲醇溶液混合·反应,而合成了金属络合物(E)。成为络合物的原料的下述配体是基于Tetrahedron.,1999,55,8377合成的。
首先,在氮气气氛下,将含有0.100g的配体的乙醇10ml溶液和含有0.042g的乙酸锰四水合物的甲醇2.5ml溶液加入25ml的梨形烧瓶中,在加热为80℃的同时搅拌5小时。将所得的溶液向饱和乙酸锰水溶液20ml中滴加,搅拌1小时。通过将所析出的固体过滤、干燥,得到了金属络合物(E)(产量0.029g)。ESI-MS[M·]+:683.1
[实施例6](金属络合物(F)的合成)
通过依照以下的反应式,将含有配体和2-乙基己酸钴的氯仿溶液混合·反应,而合成了金属络合物(F)。成为络合物的原料的下述配体是基于Tetrahedron.,1999,55,8377合成的。
在氮气气氛下,将含有0.077g的配体和0.239g的2-乙基己酸钴(65wt%矿物油溶液)的氯仿5ml加入25ml的梨形烧瓶中,在加热为60℃的同时搅拌9小时。将该溶液向二乙醚50ml的三角烧瓶中滴加。通过将所析出的固体过滤,继而用二乙醚清洗、干燥,得到了金属络合物(F)(产量0.146g)。ESI-MS[M·]+:1032.2
元素分析值(%):计算值(作为C58H66Co2N4O6);C,67.43;H,6.44;N,5.42;实测值:C,66.97;H,6.21;N,5.27。
[实施例7](金属络合物(G)的合成)
通过依照以下的反应式,将含有配体和乙酸镍四水合物的乙醇溶液混合·反应,而合成了金属络合物(G)。成为络合物的原料的下述配体是基于Tetrahedron.,1999,55,8377合成的。
在氮气气氛下,将含有0.250g的配体和0.100g的乙酸镍四水合物的30ml乙醇加入50ml的梨形烧瓶中,在80℃下搅拌2小时。通过将所生成的橙色沉淀过滤而用乙醇清洗、真空干燥,得到了金属络合物(G)(产量0.242g)。元素分析值(%):Calcd for C42H36N4NiO2;C,73.38;H,5.28;N,8.15;实测值:C,72.42;H,5.27;N,7.96。ESI-MS[M·]+:687.1.
[实施例8](金属络合物(H)的合成)
通过依照以下的反应式,将含有配体和乙酸铜一水合物的乙醇溶液混合·反应,而合成了金属络合物(H)。成为络合物的原料的下述配体是基于Tetrahedron.,1999,55,8377合成的。
在氮气气氛下,将含有0.315g的配体和0.100g的乙酸铜一水合物的30ml乙醇加入50ml的梨形烧瓶中,在80℃下搅拌2小时。通过在将所生成的赭色沉淀过滤而用乙醇清洗后,进行真空干燥,得到了金属络合物(H)(产量0.250g)。元素分析值(%):Calcd for C42H36CuN4O2;C,72.87;H,5.24;N,8.09;实测值:C,72.22;H,5.37;N,7.77。ESI-MS[M·]+:692.1.
[实施例9](金属络合物(I)的合成)
通过依照以下的反应式,将含有配体和乙酸铁的乙醇溶液混合·反应,而合成了金属络合物(I)。成为络合物的原料的下述配体是基于Tetrahedron.,1999,55,8377合成的。
在氮气气氛下,将含有0.440g的配体和0.120g的乙酸铁的30ml乙醇加入50ml的梨形烧瓶中,在80℃下搅拌2小时。通过在将所生成的橙色沉淀过滤而用乙醇清洗后,进行真空干燥,得到了金属络合物(I)(产量0.380g)。元素分析值(%):Calcd for C42H36FeN4O2;C,73.68;H,5.30;N,8.18;实测值:C,72.20;H,5.42;N,7.85。ESI-MS[M·]+:684.0.
[实施例10](金属络合物(J)的合成)
通过依照以下的反应式,将含有配体和乙酸镍的乙醇溶液混合·反应,而合成了金属络合物(J)。成为络合物的原料的下述配体是基于Tetrahedron.,1999,55,8377合成的。
在氮气气氛下,将含有0.200g的配体和0.250g的乙酸镍四水合物的30ml乙醇加入50ml的梨形烧瓶中,在加热为100℃的同时搅拌2小时后,析出了橙色固体。通过将该固体过滤,用乙醇和二乙醚清洗、干燥,得到了金属络合物(J)(产量0.276g)。元素分析值(%):作为C46H42N4Ni2O6,计算值:C,63.93;H,4.90;N,6.07;实测值:C,63.22;H,5.02;N,6.43.
[实施例11](金属络合物(K)的合成)
通过依照以下的反应式,将含有配体的氯仿溶液和含有硝酸钴六水合物的甲醇溶液混合·反应,而合成了金属络合物(K)。成为络合物的原料的下述配体是基于Tetrahedron.,1999,55,8377合成的。
在氮气气氛下,将含有0.096g的配体和0.082g的硝酸钴六水合物的氯仿2ml和甲醇5ml的混合溶液加入100ml的梨形烧瓶中,在加热为60℃的同时下搅拌7小时,生成了黄色固体。通过将该固体过滤,继而用甲醇清洗、干燥,得到了金属络合物(K)(产量0.036g)。ESI-MS[M-NO3]+:808.0。
[实施例12](金属络合物(L)的合成)
通过依照以下的反应式,将含有金属络合物(B)的氯仿/乙醇混合溶液和含有氯化铜的乙醇溶液混合·反应,而合成了金属络合物(L)。
在氮气气氛下,将含有0.066g的金属络合物(B)的氯仿1ml和乙醇2ml的混合溶液加入25ml的梨形烧瓶中,向含有0.013的氯化铜(II)的乙醇4ml中滴加。在将该溶液加热为80℃的同时,搅拌3小时。通过将所析出的固体过滤,继而用乙醇清洗、干燥,得到了金属络合物(L)(产量0.054g)。ESI-MS[M-Cl]+:787.0。
[实施例13](金属络合物(M)的合成)
通过依照以下的反应式,将含有配体和乙酸钴四水合物的乙醇溶液混合·反应,而合成了金属络合物(M)。成为络合物的原料的下述配体是基于Tetrahedron.,1999,55,8377合成的。
在氮气气氛下,将0.303g的配体和0.125g的乙酸钴四水合物加入100ml两口烧瓶中,加入50ml的乙醇。通过将该溶液回流3小时,生成了赭色固体。通过将该沉淀过滤、干燥,得到了金属络合物(M)(产量0.242g)。ESI-MS[M+H]+:664.2。
将所得的金属络合物(M)的红外线(IR)吸收光谱示于图2。
[实施例14](金属络合物(N)的合成)
通过依照以下的反应式,将含有配体和乙酸钴四水合物的乙醇溶液混合·反应,而合成了金属络合物(N)。成为络合物的原料的下述配体是基于Tetrahedron.,1999,55,8377合成的。
在氮气气氛下,将0.303g的配体和0.324g的乙酸钴四水合物加入100ml两口烧瓶中,加入20ml的乙醇和20ml的氯仿混合溶液。通过将该溶液回流3小时,生成了赭色固体。通过将该沉淀过滤、干燥,得到了金属络合物(N)(产量0.133g)。ESI-MS[M-OAc]+:781.0。将所得的金属络合物(N)的红外线(IR)吸收光谱表示于图3中。
依照以下的反应式,通过化合物(O)、配体(P)合成了金属络合物(Q)。
[合成例1](化合物(O)的合成)
在氩气气氛下,将3.945g的2,9-二(3’-溴-5’-叔丁基-2’-甲氧基苯基)-1,10-菲咯啉、3.165g的1-N-Boc-吡咯-2-硼酸、0.138g的三(亚苄基丙酮)二钯、0.247g的2-环己基膦基-2’,6’-二甲氧基联苯、5.527g的磷酸钾溶解于200mL的二噁烷和20mL的水的混合溶剂中,在60℃下搅拌6小时。反应结束后,自然冷却,加入蒸馏水、氯仿,萃取有机层。将所得的有机层浓缩,得到黑色的残渣。将其使用硅胶柱提纯,得到化合物(O)。1H-NMR(300MHz,CDCl3)δ1.34(s,18H),1.37(s,18H),3.30(s,6H),6.21(m,2H),6.27(m,2H),7.37(m,2H),7.41(s,2H),7.82(s,2H),8.00(s,2H),8.19(d,J=8.6Hz,2H),8.27(d,J=8.6Hz,2H).
[合成例2](化合物(P)的合成)
在氮气气氛下,将0.904g的化合物(O)溶解于10mL的无水二氯甲烷中。在将二氯甲烷溶液冷却为-78℃的同时,慢慢地滴加8.8mL的三溴化硼(1.0M二氯甲烷溶液)。滴加后,原样不动地搅拌10分钟后,在搅拌至室温的同时,放置。3小时后,将反应溶液冷却到0℃,加入饱和NaHCO3水溶液后,加入氯仿萃取,将有机层浓缩。将所得的褐色的残渣用硅胶柱提纯,得到配体(P)。1H-NMR(300MHz,CDCl3)δ1.40(s,18H),6.25(m,2H),6.44(m,2H),6.74(m,2H),7.84(s,2H),7.89(s,2H),7.92(s,2H),8.35(d,J=8.4Hz,2H),8.46(d,J=8.4Hz,2H),10.61(s,2H),15.88(s,2H).
[实施例15](金属络合物(Q)的合成)
在氮气气氛下,将含有0.100g的配体(P)和0.040g的乙酸钴四水合物的20ml用Ar脱气了的乙腈溶液加入100ml两口烧瓶中,在室温下搅拌。向该溶液中滴加45μl三乙胺,回流3小时。通过在将该溶液浓缩、冷却后,用薄膜过滤器过滤、干燥,得到了金属络合物(Q)(产量0.098g)。ESI-MS[M·]+:663.1。
依照以下的反应式,经由化合物(R)、配体(S)合成了金属络合物(T)。
[合成例3](化合物(R)的合成)
在氩气气氛下,将0.662g的2,9-二(3’-溴-5’-叔丁基-2’-甲氧基苯基)-1,10-菲咯啉、0.320g的2-噻吩基硼酸、0.090g的三(亚苄基丙酮)二钯、0.160g的2-环己基膦基-2’,6’-二甲氧基联苯、0.920g的磷酸钾溶解于30mL的二噁烷和5mL的水的混合溶剂中,在80℃下搅拌12小时。反应结束后,自然冷却,加入蒸馏水、氯仿,萃取有机层。将所得的有机层浓缩,得到黑色的残渣。将其使用硅胶柱提纯后,利用重结晶得到化合物(R)。1H-NMR(300MHz,CDCl3)δ1.42(s,18H),3.48(s,6H),7.12(dd,2H),7.38(d,J=5.0Hz,2H),7.52(d,J=2.9Hz,2H),7.73(s,2H),7.87(s,2H),7.98(s,2H),8.28(d,J=8.6Hz,2H),8.30(d,J=8.6Hz,2H).
[合成例4](配体(S)的合成)
在氮气气氛下,将0.134g的化合物(R)溶解于5mL的乙酸中。滴加48%氢溴酸0.337g,在120℃下搅拌。20小时后,将反应溶液冷却到0℃,加入水后,加入氯仿而萃取,将有机层浓缩。将所得的残渣用硅胶柱提纯,得到配体(S)。1H-NMR(300MHz,CDCl3)δ1.40(s,18H),6.25(m,2H),6.44(m,2H),6.74(m,2H),7.84(s,2H),7.89(s,2H),7.92(s,2H),8.35(d,J=8.4Hz,2H),8.46(d,J=8.4Hz,2H),10.61(s,2H),15.88(s,2H).
[实施例16](金属络合物(T)的合成)
在氮气气氛下,将含有0.062g的配体(S)和0.025g的乙酸钴四水合物的氯仿2ml和乙醇6ml的混合溶液加入25ml的梨形烧瓶中,在加热为60℃的同时搅拌2小时,生成了褐色固体。通过将该固体过滤,继而用乙醇清洗、干燥,得到了金属络合物(T)(产量0.034g)。ESI-MS[M·]+:697.0。
依照以下的反应式,通过化合物(U)、配体(V)合成了金属络合物(W)。
[合成例5](化合物(U)的合成)
在氩气气氛下,将0.132g的2,9-二(3’-溴-5’-叔丁基-2’-甲氧基苯基)-1,10-菲咯啉、0.061g的3-吡啶基硼酸、0.046g的四(三苯基膦基)钯、0.111g的碳酸钾溶解于5mL的二噁烷和0.5mL的水的混合溶剂中,在100℃下搅拌9小时。反应结束后,自然冷却,加入蒸馏水、氯仿,萃取有机层。将所得的有机层浓缩,得到黑色的残渣。将其使用硅胶柱提纯后,利用重结晶得到化合物(U)。
[合成例6](配体(V)的合成)
在氮气气氛下,将0.110g的化合物(U)溶解于3mL的无水二氯甲烷中。在将二氯甲烷溶液用干冰/丙酮浴冷却为-78℃的同时,慢慢地滴加1.3mL的三溴化硼(1.0M二氯甲烷溶液)。滴加后,原样不动地搅拌10分钟后,去除干冰/丙酮浴,在搅拌至室温的同时放置。4小时后,加入饱和NaHCO3水溶液进行中和,加入氯仿而萃取3次。将所得的有机层浓缩,将所得的残渣提纯,得到配体(V)。1H-NMR(300MHz,CDCl3)δ1.47(s,18H),7.44(t,J=6.2Hz,2H),7.55(s,2H),7.95(s,2H),8.16(s,2H),8.40(d,J=8.3Hz,2H),8.53(d,J=8.4Hz,2H),8.67(d,J=7.5Hz,2H),9.47(s,2H),9.79(d,J=2.8z,2H),15.36(s,2H).
[实施例17](金属络合物(W)的合成)
在氮气气氛下,将含有0.096g的配体(V)和0.037g的乙酸钴四水合物的氯仿10ml和乙醇4ml的混合溶液加入100ml的梨形烧瓶中,在加热为60℃的同时搅拌6小时,生成了褐色固体。通过将该固体过滤,继而用乙醇清洗、干燥,得到了金属络合物(W)(产量0.040g)。ESI-MS[M·]+:687.1。将所得的金属络合物(W)的红外线(IR)吸收光谱表示于图4中。
[比较例1](金属络合物(X)的合成)
依照以下的反应式合成了金属络合物(X)。
首先,在氮气气氛下,将含有0.476g的氯化钴六水合物和0.412g的4-叔丁基-2,6-二甲酰基苯酚的10ml乙醇溶液加入50ml的梨形烧瓶中,在室温下搅拌。向该溶液中慢慢地添加含有0.216g的邻苯二胺的5ml乙醇溶液。通过将上述混合物回流2小时,生成了茶褐色沉淀。通过将该沉淀过滤、干燥,得到金属络合物(X)(产量0.465g)。元素分析值(%):计算值(作为C36H38Cl2Co2N4O4);C,55.47;H,4.91;N,7.19.实测值:C,56.34;H,4.83;N,7.23。
[比较例2](金属络合物(Y)的合成)
依照Australian Journal of Chemistry,23,2225(1970)中所示的方法,合成下述反应式所示的金属络合物(Y)
首先,在氮气气氛下,将含有1.9g的氯化钴六水合物和1.31g的4-叔丁基-2,6-二甲酰基苯酚的50ml甲醇溶液加入到100ml的梨形烧瓶中,在室温下进行搅拌。向该溶液中慢慢加入含有0.59gl,3-丙二胺的20ml甲醇。通过将上述混合物回流3小时,生成茶褐色沉淀。通过将该沉淀过滤、干燥,得到金属络合物(Y)(产量1.75g)。元素分析值(%):计算值(作为C26H34Cl2Co2N4O4);C,47.65;H,5.23;N,8.55.实测值:C,46.64;H,5.02;N,8.58。
[比较例3](金属络合物(Z)的合成)
依照Bulletin of Chemical Society of Japan,68,1105,(1995).中记载的方法,合成了下述的反应式中所示的金属络合物(Z)。
将含有0.33g的4-甲基-2,6-二甲酰基苯酚和0.49g的乙酸锰四水合物的10ml的甲醇加入50ml的梨形烧瓶中,在室温下搅拌。向该溶液中慢慢地添加含有0.15g的1,3-丙二胺的5ml甲醇。将上述混合物搅拌1小时后,生成了黄色沉淀。通过在将该沉淀过滤,用甲醇清洗后,进行真空干燥,得到了金属络合物(Z)(产量0.25g)。元素分析值(%):计算值(作为C28H32Mn2N4O6);C,53.34;H,5.12;N,8.89.实测值:C,53.07;H,5.12;N,8.72。
[比较例4](金属络合物(AA)的合成)
通过依照以下的反应式,将含有希夫式碱配体的氯仿和含有乙酸钴四水合物的乙醇混合·反应,而合成了金属络合物(AA)。依照A Chemistry,European Journal,1999,5,1460合成了成为络合物的原料的希夫式碱配体及金属络合物(AA)。
在氮气气氛下,将含有0.303g的邻苯二胺和1.00g的4-叔丁基-2-甲酰基苯酚的10ml乙醇溶液加入50ml的梨形烧瓶中,在80℃下搅拌3小时。过滤析出的橙色沉淀,进行清洗及干燥,得到希夫式碱配体。(产量0.838g)。1H-NMR;δ:12.83(s,2H),8.64(s,2H),7.41(d,J=8.7Hz,2H),7.36-7.32(m,4H),7.25-7.21(m,4H),6.99(d:8.7Hz,2H),1.32(s,18H)。
接下来,通过将含有上述希夫式碱配体的氯仿和含有乙酸钴四水合物的乙醇混合、反应,合成了金属络合物(AA)。
向加入了含有0.214g的上述希夫式碱配体的3ml的氯仿溶液的25ml梨形烧瓶中,一边搅拌一边加入含有0.125g的乙酸钴四水合物的7ml的乙醇,在室温下搅拌6小时。将析出的褐色沉淀过滤,用乙醇清洗后,真空干燥,得到金属络合物(AA)。(产量0.138g)。元素分析值(%):Calcd forC28H34CoN2O4;C,64.49;H,6.57;N,5.37.实测值:C,64.92;H,6.13;N,5.06.ESI-MS[M·]+:485.1。
[实施例24](金属络合物(A)的耐酸性试验)
(1)对本发明的金属络合物(A),进行了对使用了硫酸的酸的耐受性试验。取7.90mg的金属络合物(A),溶解于36mL甲醇中。取9.0mL溶液,加入1M硫酸水溶液1.0mL。快速地搅拌后,采取0.3mL,将稀释为10倍的溶液加入吸收池中,将盖子关闭,加热为60℃。使用分光光度计(Varian公司制,Cary5E),观察了溶液的紫外可见吸收的经时变化。将359nm的波长下的吸光度及自刚刚滴加后不久起的吸光度比表示于表1中。根据该结果判明,本发明的金属络合物(A)即使在酸的存在下,在实质上也看不到吸光度的减少,是稳定性优异的化合物。
表1
359nm的吸光度 | 吸光度比 | |
刚刚滴加后不久 | 0.475 | 1.00 |
30分钟后 | 0.477 | 1.00 |
1小时后 | 0.489 | 1.03 |
2小时后 | 0.497 | 1.04 |
3小时后 | 0.509 | 1.07 |
[实施例25](金属络合物(B)的耐酸性试验)
将金属络合物(A)置换为金属络合物(B),进行与上述相同的操作,观察了UV吸收的经时变化。将444nm的波长下的吸光度及自刚刚滴加后不久起的吸光度比表示于表2中。根据该结果判明,本发明的金属络合物(B)即使在酸的存在下,在实质上也看不到吸光度的减少,是稳定性优异的化合物。
表2
444nm的吸光度 | 吸光度比 | |
刚刚滴加后不久 | 0.103 | 1.00 |
30分钟后 | 0.105 | 1.00 |
1小时后 | 0.104 | 1.02 |
2小时后 | 0.106 | 1.03 |
3小时后 | 0.108 | 1.05 |
[实施例26](金属络合物(D)的耐酸性试验)
将金属络合物(A)置换为金属络合物(D),进行与上述相同的操作,观察了UV吸收的经时变化。将441nm的波长下的吸光度及自刚刚滴加后不久起的吸光度比表示于表3中。根据该结果判明,本发明的金属络合物(D)即使在酸的存在下,在实质上也看不到吸光度的减少,是稳定性优异的化合物。
表3
441nm的吸光度 | 吸光度比 | |
刚刚滴加后不久 | 0.075 | 1.00 |
30分钟后 | 0.075 | 1.00 |
1小时后 | 0.075 | 0.99 |
2小时后 | 0.077 | 1.02 |
3小时后 | 0.075 | 1.00 |
[实施例27](金属络合物(I)的耐酸性试验)
将金属络合物(A)置换为金属络合物(I),进行与上述相同的操作,观察了UV吸收的经时变化。将547nm的波长下的吸光度及自刚刚滴加后不久起的吸光度比表示于表4中。根据该结果判明,本发明的金属络合物(I)即使在酸的存在下,在实质上也看不到吸光度的减少,是稳定性优异的化合物。
表4
547nm的吸光度 | 吸光度比 | |
刚刚滴加后不久 | 0.065 | 1.00 |
30分钟后 | 0.066 | 1.00 |
1小时后 | 0.067 | 1.03 |
2小时后 | 0.066 | 1.00 |
3小时后 | 0.072 | 1.10 |
[比较例5]
为了比较,将金属络合物(A)置换为比较例的金属络合物(X),进行与上述相同的操作,观察了UV吸收的经时变化。将455nm的波长下的吸光度及自刚刚滴加后不久起的吸光度比表示于表5中。比较例的金属络合物(X)在酸的存在下,吸光度随时间推移而大幅度减少,说明络合物分解。
表5
455nm的吸光度 | 吸光度比 | |
刚刚滴加后不久 | 0.363 | 1.00 |
30分钟后 | 0.366 | 1.01 |
1小时后 | 0.326 | 0.90 |
2小时后 | 0.265 | 0.73 |
3小时后 | 0.136 | 0.37 |
[实施例28](络合物的耐热性试验)
对金属络合物(A)、(B)、(D)及(L),使用热重/示差热分析装置(精工仪器公司制、EXSTAR-6300),对各个金属络合物,测定在400~800℃的范围中热处理时的质量变化(TGA),根据与供测定用的初期质量的比率求出质量减少率。测定条件是在氮气气氛下,40~800℃(升温速度10℃/min),在热处理中使用了氧化铝皿。将800℃的质量减少率表示于表6中。
[比较例6]
为了比较,在实施例28中,将金属络合物(A)置换为金属络合物(X)、(Y)、(Z)、(AA)或(AB),使用热重/示差热分析装置(精工仪器公司制、EXSTAR-6300),进行了与实施例28相同的实验。将质量减少率表示于表6中。而且,上述金属络合物(AB)作为比较例,是将实施例28的金属络合物(A)置换为N,N’-二水杨醛乙二胺铁(II)络合物(TCI公司制)的例子。
根据表6,如果将本发明的金属络合物(A)、(B)、(D)及(L)分别与比较例的相同种类及相同核数的金属络合物比较,则哪一个的质量减少率都小于比较例,判明耐热性优异。
表6
800℃的质量减少率(%) | |
金属络合物(A) | 29.98 |
金属络合物(B) | 35.57 |
金属络合物(D) | 32.45 |
金属络合物(L) | 33.18 |
金属络合物(X) | 36.71 |
金属络合物(Y) | 50.41 |
金属络合物(Z) | 42.60 |
金属络合物(AA) | 58.00 |
金属络合物(AB) | 65.00 |
[实施例29](金属络合物(D)的过氧化氢分解试验)
在两口烧瓶中量取金属络合物(D)3.4mg(约8μmol(每1个金属原子)),向其中作为溶剂加入酒石酸/酒石酸钠缓冲溶液(由1.00ml(0.20mol/l酒石酸水溶液和0.10mol/l酒石酸钠水溶液配制,pH4.0)和乙二醇(1.00ml),搅拌。将其作为催化剂混合溶液使用。
在加入了该催化剂混合溶液的两口烧瓶的一个口上安装隔膜,将另一个口与气体量管连结。将该烧瓶在80℃下搅拌5分钟后,用注射器加入过氧化氢水溶液(11.4mol/l、0.20ml(2.28mmol)),在80℃下进行20分钟过氧化氢分解反应。利用气体量管测定产生的氧,将分解了的过氧化氢定量。
被分解了的过氧化氢量是根据在该过氧化氢分解试验中产生的含有氧的气体体积求出的。利用下式,将实测的产生气体体积值v换算为考虑了水蒸气压的0℃、101325Pa(760mmHg)下的气体体积V。
将结果示于图5。确认了,与后述的空白试验相比较,本发明的金属络合物(D)的发生气体体积量高,具有过氧化氢分解中的催化剂效果。
(式中,P:大气压(mmHg)、p:水的蒸气压(mmHg)、t:温度(℃)、v:实测的产生气体体积(ml)、V:0℃、101325Pa(760mmHg)下的气体体积)ml。)
[空白试验]
向两口烧瓶中作为溶剂加入酒石酸/酒石酸钠缓冲溶液1.00ml(由0.20mol/l酒石酸水溶液和0.10mol/l酒石酸钠水溶液配制,pH4.0)和乙二醇1.00ml。在该两口烧瓶的一个口上安装隔膜,将另一个口与气体量管连结。将该烧瓶在80℃下搅拌5分钟后,加入过氧化氢水溶液(11.4mol/l、0.200ml(2.28mmol)),在80℃下反应20分钟,利用气体量管将所产生的过氧化氢定量。
可以认为,本空白试验主要检测出溶解于溶液中的空气等。
[比较例7](金属络合物(Z)的过氧化氢分解试验)
除了将实施例29的金属络合物(D)变更为金属络合物(Z)以外,进行了与实施例29同等的试验。将结果与实施例29一起表示于图5中。
产生气体体积与空白实验没有差别,看不到过氧化氢分解的催化效果。
工业上的利用可能性
本发明的金属络合物由于稳定性(例如耐热性、耐酸性等)优异,因此对于氧化还原反应催化等十分有用。所以,该金属络合物即使在高温下或强酸的存在下,也可以抑制催化活性的降低,能够成为应用用途宽的催化剂,因此在工业上十分有用。
虽然将本发明与其实施方式一起进行了说明,然而只要我们没有特别指定,则在说明的任何部分中都并非想要限定我们的发明,应当不违反附加的权利要求要求的范围中所示的发明的精神和范围地得到宽范围的解释。
Claims (7)
1.一种下式(1)所示的金属络合物,
式中,R1~R6各自独立地表示氢原子或取代基,R1与R2、R2与R3、R4与R5及/或R5与R6也可以相互结合形成环;Y1及Y2各自独立地表示
其中,Rα是氢原子或碳数为1~4的烃基;P1是与Y1和Y1的邻位的2个碳原子成为一体形成杂环所必需的原子组,P2是与Y2和Y2的邻位的2个碳原子成为一体形成杂环所必需的原子组,P1与P2也可以相互结合而形成环;M表示周期表中记载的过渡金属元素或典型金属元素;m表示1或2,m为2时,2个M既可以相同也可以不同;X是平衡离子或中性分子,n是处于络合物中的X的个数,表示0以上的整数,X有多个时,既可以相同也可以不同;Q1及Q2各自独立地表示芳香族杂环基。
3.根据权利要求1或2所述的金属络合物,其中,在所述式(1)或(2)中,m为2,M是周期表记载的第3族~第9族的过渡金属元素。
4.根据权利要求1或2所述的金属络合物,其中,所述式(1)或(2)中,m为1。
5.一种聚合物,其具有所述式(1)或(2)所示的金属络合物的残基。
6.根据权利要求5所述的聚合物,其中,具有所述式(1)或(2)所示的金属络合物的残基作为重复单元。
7.一种催化剂,其为使用权利要求1~6中任一项所述的金属络合物及/或聚合物而得。
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CN114621259A (zh) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | 一种金属有机氢化物络合物材料及其制备方法与应用 |
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JP5422159B2 (ja) * | 2007-12-28 | 2014-02-19 | 住友化学株式会社 | 環状化合物、その金属錯体及び変性金属錯体 |
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