JP2016124824A - Reductant and method for producing metal using the same - Google Patents
Reductant and method for producing metal using the same Download PDFInfo
- Publication number
- JP2016124824A JP2016124824A JP2014266775A JP2014266775A JP2016124824A JP 2016124824 A JP2016124824 A JP 2016124824A JP 2014266775 A JP2014266775 A JP 2014266775A JP 2014266775 A JP2014266775 A JP 2014266775A JP 2016124824 A JP2016124824 A JP 2016124824A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- group
- reducing agent
- dihydropyrazine
- solvent
- 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.)
- Granted
Links
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 8
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims abstract description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 abstract description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 55
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000010949 copper Substances 0.000 description 10
- 239000002082 metal nanoparticle Substances 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 8
- -1 tert-butylsilyl Chemical group 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 7
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 6
- FINHMKGKINIASC-UHFFFAOYSA-N Tetramethylpyrazine Chemical compound CC1=NC(C)=C(C)N=C1C FINHMKGKINIASC-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 5
- 230000033116 oxidation-reduction process Effects 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- PGIXYGKJSGJQCR-UHFFFAOYSA-L dichlorocopper oxolane Chemical compound Cl[Cu]Cl.C1CCOC1 PGIXYGKJSGJQCR-UHFFFAOYSA-L 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- VWTVTOBJLRBNMT-UHFFFAOYSA-N trimethyl-(2,3,5,6-tetramethyl-4-trimethylsilylpyrazin-1-yl)silane Chemical compound CC1=C(C)N([Si](C)(C)C)C(C)=C(C)N1[Si](C)(C)C VWTVTOBJLRBNMT-UHFFFAOYSA-N 0.000 description 2
- XYNBEQAWBCGIMD-UHFFFAOYSA-N 1,4-dihydropyrazine Chemical compound N1C=CNC=C1 XYNBEQAWBCGIMD-UHFFFAOYSA-N 0.000 description 1
- UYXIFSCWRIQATQ-UHFFFAOYSA-N 2,3,5,6-tetramethyl-1,4-dihydropyrazine Chemical compound CC1=C(C)NC(C)=C(C)N1 UYXIFSCWRIQATQ-UHFFFAOYSA-N 0.000 description 1
- RYKLZUPYJFFNRR-UHFFFAOYSA-N 3-hydroxypiperidin-2-one Chemical compound OC1CCCNC1=O RYKLZUPYJFFNRR-UHFFFAOYSA-N 0.000 description 1
- XNWQOBGVVHLPFY-UHFFFAOYSA-N 4-butyl-1H-pyrazine Chemical compound CCCCN1C=CNC=C1 XNWQOBGVVHLPFY-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- PKQYMLHWBGWVAQ-UHFFFAOYSA-N C(C(C)C)[Si](N1C=CN(C=C1)[Si](CC(C)C)(CC(C)C)CC(C)C)(CC(C)C)CC(C)C Chemical compound C(C(C)C)[Si](N1C=CN(C=C1)[Si](CC(C)C)(CC(C)C)CC(C)C)(CC(C)C)CC(C)C PKQYMLHWBGWVAQ-UHFFFAOYSA-N 0.000 description 1
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- 102100027617 DNA/RNA-binding protein KIN17 Human genes 0.000 description 1
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- 101100398255 Homo sapiens KIN gene Proteins 0.000 description 1
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- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- LDKSTCHEYCNPDS-UHFFFAOYSA-L carbon monoxide;dichloroplatinum Chemical compound O=C=[Pt](Cl)(Cl)=C=O LDKSTCHEYCNPDS-UHFFFAOYSA-L 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- ITFUHOHJQIDNQW-UHFFFAOYSA-L copper;2,2-dimethylpropanoate Chemical compound [Cu+2].CC(C)(C)C([O-])=O.CC(C)(C)C([O-])=O ITFUHOHJQIDNQW-UHFFFAOYSA-L 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- PKELYQZIUROQSI-UHFFFAOYSA-N phosphane;platinum Chemical compound P.[Pt] PKELYQZIUROQSI-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 229940071240 tetrachloroaurate Drugs 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- MYPPRJDQOICMRN-UHFFFAOYSA-N tri(butan-2-yl)-[2,3,5,6-tetramethyl-4-tri(butan-2-yl)silylpyrazin-1-yl]silane Chemical compound CC=1N(C(=C(N(C1C)[Si](C(C)CC)(C(C)CC)C(C)CC)C)C)[Si](C(C)CC)(C(C)CC)C(C)CC MYPPRJDQOICMRN-UHFFFAOYSA-N 0.000 description 1
- YSTXNQLMGXPNFY-UHFFFAOYSA-N tri(propan-2-yl)-[2,3,5,6-tetramethyl-4-tri(propan-2-yl)silylpyrazin-1-yl]silane Chemical compound CC=1N(C(=C(N(C1C)[Si](C(C)C)(C(C)C)C(C)C)C)C)[Si](C(C)C)(C(C)C)C(C)C YSTXNQLMGXPNFY-UHFFFAOYSA-N 0.000 description 1
- MIVDSZBKWSDLHZ-UHFFFAOYSA-N tri(propan-2-yl)-[4-tri(propan-2-yl)silylpyrazin-1-yl]silane Chemical compound CC(C)[Si](C(C)C)(C(C)C)N1C=CN([Si](C(C)C)(C(C)C)C(C)C)C=C1 MIVDSZBKWSDLHZ-UHFFFAOYSA-N 0.000 description 1
- KXTRFERTONKOGV-UHFFFAOYSA-N tributyl-(2,3,5,6-tetraethyl-4-tributylsilylpyrazin-1-yl)silane Chemical compound C(C)C=1N(C(=C(N(C1CC)[Si](CCCC)(CCCC)CCCC)CC)CC)[Si](CCCC)(CCCC)CCCC KXTRFERTONKOGV-UHFFFAOYSA-N 0.000 description 1
- SSDZBWATFCBBSD-UHFFFAOYSA-N triethyl-(2,3,5,6-tetraethyl-4-triethylsilylpyrazin-1-yl)silane Chemical compound C(C)C=1N(C(=C(N(C1CC)[Si](CC)(CC)CC)CC)CC)[Si](CC)(CC)CC SSDZBWATFCBBSD-UHFFFAOYSA-N 0.000 description 1
- LDFZGKLEQBHNLQ-UHFFFAOYSA-N trimethyl-(4-trimethylsilylcyclohexa-2,5-dien-1-yl)silane Chemical compound C[Si](C)(C)C1C=CC([Si](C)(C)C)C=C1 LDFZGKLEQBHNLQ-UHFFFAOYSA-N 0.000 description 1
- WGBPOPJACTZYSA-UHFFFAOYSA-N trimethyl-(4-trimethylsilylpyrazin-1-yl)silane Chemical compound C[Si](C)(C)N1C=CN([Si](C)(C)C)C=C1 WGBPOPJACTZYSA-UHFFFAOYSA-N 0.000 description 1
- POXYGXWWPXLRCP-UHFFFAOYSA-N tripropyl-(2,3,5,6-tetrabutyl-4-tripropylsilylpyrazin-1-yl)silane Chemical compound C(CCC)C=1N(C(=C(N(C1CCCC)[Si](CCC)(CCC)CCC)CCCC)CCCC)[Si](CCC)(CCC)CCC POXYGXWWPXLRCP-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
本発明は、新規な還元剤およびそれを用いた金属の製造方法に関し、さらに詳しくは溶媒中での還元反応によって金属イオンを還元し得る還元剤およびそれを用いる金属の製造方法に関する。 The present invention relates to a novel reducing agent and a method for producing a metal using the same, and more particularly to a reducing agent capable of reducing metal ions by a reduction reaction in a solvent and a method for producing a metal using the same.
金属および金属ナノ粒子の製造方法としては、金属固体を加熱して発生させた蒸気に不活性ガス分子などを衝突させて急冷することによって微細化する蒸発法が知られている。 この方法によれば、高濃度で且つ高純度の金属ナノ粒子を得ることができる。しかし、原料である金属固体から蒸気を発生させるための設備が必要である。そこで、このような特別な設備を必要としない金属ナノ粒子の製造方法として、溶媒中で金属塩を還元して金属ナノ粒子を製造する技術が注目されている。 As a method for producing metal and metal nanoparticles, there is known an evaporation method in which a metal solid is heated and heated to make an inert gas molecule collide with an inert gas molecule and rapidly cooled. According to this method, high-concentration and high-purity metal nanoparticles can be obtained. However, equipment for generating steam from a metal solid as a raw material is necessary. Therefore, as a method for producing metal nanoparticles that do not require such special equipment, a technique for producing metal nanoparticles by reducing a metal salt in a solvent has attracted attention.
例えば、特許文献１には、金属イオンを含有する溶液、有機分子からなる保護剤を含有する溶液および還元剤を含有する溶液を溶媒に滴下して還元することにより、有機分子で保護した金属ナノ粒子集合体を沈降させて回収する金属ナノ粒子の製造方法が記載されており、具体例として水素化ホウ素ナトリウムを還元剤として用いて金属イオンを還元し、金属を含む沈殿物を得た例が示されている。 For example, Patent Document 1 discloses that a metal nanoparticle protected with an organic molecule by dropping a solution containing a metal ion, a solution containing a protective agent composed of organic molecules, and a solution containing a reducing agent by dropping them into a solvent. A method for producing metal nanoparticles for collecting and recovering particle aggregates is described. As a specific example, a metal ion is reduced using sodium borohydride as a reducing agent to obtain a precipitate containing metal. It is shown.
しかし、前記特許文献１に示されている還元剤である水素化ホウ素ナトリウムは、標準酸化還元電位が−０．４８Ｖを示す（例えば、Ｂｒｉａｎ Ｌ． Ｃｕｓｈｉｎｇ、 Ｖｌａｄｉｍｉｒ Ｌ． Ｋｏｌｅｓｎｉｃｈｅｎｋｏ， ａｎｄ Ｃｈａｒｌｅｓ Ｊ． Ｏ’Ｃｏｎｎｏｒ， Ｃｈｅｍ． Ｒｅｖ． ２００４，１０４，３８９３−３９４６）ことから、標準酸化還元電位が−０．４８Ｖ未満の金属イオン、例えばＧａ３＋（Ｇａ／Ｇａ３＋の標準酸化還元電位＝−０．５２９Ｖ、化学便覧改訂４版 基礎編II II−４６６）の還元によって金属Ｇａを得ることは理論的に不可能である。また、水素化ホウ素ナトリウムを還元剤として用いて金属を形成すると、還元剤がＮａを含むため還元して得られる夾雑物が塩となり得る。 However, sodium borohydride, which is a reducing agent disclosed in Patent Document 1, exhibits a standard oxidation-reduction potential of −0.48 V (for example, Brian L. Cushing, Vladimir L. Kolesnichenko, and Charles J. O). Rev. 2004, 104, 3893-3946), a metal ion having a standard redox potential of less than −0.48 V, for example, Ga 3+ (standard redox potential of Ga / Ga 3 + = − 0.529 V). It is theoretically impossible to obtain metallic Ga by the reduction of Chemical Handbook 4th edition, basic edition II II-466). Further, when sodium borohydride is used as a reducing agent to form a metal, since the reducing agent contains Na, impurities obtained by reduction can become a salt.
従って、本発明の目的は、溶媒中での還元反応によって金属イオンを還元し得る新規な還元剤を提供することである。
また、本発明の他の目的は、溶媒中で前記還元剤を用いる金属の製造方法を提供することである。
Accordingly, an object of the present invention is to provide a novel reducing agent capable of reducing metal ions by a reduction reaction in a solvent.
Another object of the present invention is to provide a method for producing a metal using the reducing agent in a solvent.
第１の発明は、下記一般式で示される化合物からなる還元剤に関する。
（前記式中、Ｘ１およびＸ２はそれぞれ同一であるか又は異なって窒素原子あるいはメチン基であり、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６はそれぞれ同一であるか又は異なって水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基又はｔｅｒｔ−ブチル基である。） (In the above formulas, X 1 and X 2 are the same or different and are nitrogen atoms or methine groups, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same, respectively. Or a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.
第２の発明は、Ｘ１およびＸ２がそれぞれ窒素原子である前記の還元剤に関する。
第３の発明は、金属イオンの還元に用いられる前記の還元剤に関する。
第４の発明は、前記のいずれかの還元剤と金属イオン源とを溶媒中で接触させる金属の製造方法に関する。
第５の発明は、前記金属が、粒子又は薄膜の形態である前記金属の製造方法に関する。
第６の発明は、前記接触が、室温で行われる前記金属の製造方法に関する。
第７の発明は、前記金属が、Ｇａである前記のいずれかに記載の金属の製造方法に関する。
第８の発明は、前記金属が、ＧａとＧａイオンよりも高い標準酸化還元電位を有する少なくとも１種の金属との合金である前記金属の製造方法に関する。
The second invention relates to the above reducing agent wherein X 1 and X 2 are each a nitrogen atom.
3rd invention is related with the said reducing agent used for reduction | restoration of a metal ion.
4th invention is related with the manufacturing method of the metal which makes any one of said reducing agents and metal ion sources contact in a solvent.
5th invention is related with the manufacturing method of the said metal whose said metal is a form of a particle | grain or a thin film.
6th invention is related with the manufacturing method of the said metal with which the said contact is performed at room temperature.
7th invention is related with the manufacturing method of the metal in any one of the said that the said metal is Ga.
The eighth invention relates to a method for producing the metal, wherein the metal is an alloy of Ga and at least one metal having a higher standard oxidation-reduction potential than Ga ions.
本発明によれば、溶媒中での還元反応によって金属イオンを還元し得る新規な還元剤を提供し得る。
また、本発明によれば、溶媒中で前記還元剤を用いて金属を容易に得ることができる。
ADVANTAGE OF THE INVENTION According to this invention, the novel reducing agent which can reduce | restore a metal ion by the reductive reaction in a solvent can be provided.
Moreover, according to the present invention, the metal can be easily obtained using the reducing agent in a solvent.
本発明の還元剤は、下記一般式で示される化合物からなる。
（前記式中、Ｘ１およびＸ２はそれぞれ同一であるか又は異なって窒素原子あるいはメチン基であり、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６はそれぞれ同一であるか又は異なって水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基又はｔｅｒｔ−ブチル基である。） (In the above formulas, X 1 and X 2 are the same or different and are nitrogen atoms or methine groups, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same, respectively. Or a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.
前記一般式で示される化合物として、例えば、１，４−ビス（トリメチルシリル）−１，４−ジヒドロピラジン、１，４−ビス（トリエチルシリル）−１，４−ジヒドロピラジン、１，４−ビス（トリｎ−プロピルシリル）−１，４−ジヒドロピラジン、１，４−ビス（トリイソプロピルシリル）−１，４−ジヒドロピラジン、１，４−ビス（ｎ−ブチルシリル）−１，４−ジヒドロピラジン、１，４−ビス（トリイソブチルシリル）−１，４−ジヒドロピラジン、１，４−ビス（トリｓｅｃ−ブチルシリル）−１，４−ジヒドロピラジン、１，４−ビス（トリｔｅｒｔ−ブチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラメチル １，４−ビス（トリメチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラメチル １，４−ビス（トリエチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラメチル １，４−ビス（トリｎ−プロピルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラメチル １，４−ビス（トリイソプロピルシリル）−１，４−ジヒドロピラジン、１，４−ビス（トリｎ−ブチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラメチル １，４−ビス（トリイソブチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラメチル １，４−ビス（トリｓｅｃ−ブチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラメチル １，４−ビス（トリｔｅｒｔ−ブチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラエチル １，４−ビス（トリメチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラエチル １，４−ビス（トリエチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラエチル １，４−ビス（トリｎ−プロピルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラエチル １，４−ビス（トリイソプロピルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラエチル １，４−ビス（トリｎ−ブチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラエチル １，４−ビス（トリイソブチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラエチル １，４−ビス（トリｓｅｃ−ブチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラエチル １，４−ビス（トリｔｅｒｔ−ブチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラｎ−プロピル １，４−ビス（トリメチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトライソプロピル １，４−ビス（トリメチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラｎ−ブチル １，４−ビス（トリｎ−プロピルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラｓｅｃ−ブチル １，４−ビス（トリメチルシリル）−１，４−ジヒドロピラジン、２，３，５，６−テトラｔｅｒｔ−ブチル １，４−ビス（トリメチルシリル）−１，４−ジヒドロピラジンや、３，６−ビス（トリメチルシリル）シクロヘキサン−１，４−ジエン（ＢＴＣＤ）、（２−メチルシクロヘキサ−２，５−ジエン−１，４−ジイル）ビス（トリメチルシラン）（ＭＢＴＣＤ）などのメチン系化合物が挙げられる。 Examples of the compound represented by the general formula include 1,4-bis (trimethylsilyl) -1,4-dihydropyrazine, 1,4-bis (triethylsilyl) -1,4-dihydropyrazine, 1,4-bis ( Tri-n-propylsilyl) -1,4-dihydropyrazine, 1,4-bis (triisopropylsilyl) -1,4-dihydropyrazine, 1,4-bis (n-butylsilyl) -1,4-dihydropyrazine, 1,4-bis (triisobutylsilyl) -1,4-dihydropyrazine, 1,4-bis (trisec-butylsilyl) -1,4-dihydropyrazine, 1,4-bis (tritert-butylsilyl) -1 , 4-dihydropyrazine, 2,3,5,6-tetramethyl 1,4-bis (trimethylsilyl) -1,4-dihydropyrazine, 2,3,5,6-teto Methyl 1,4-bis (triethylsilyl) -1,4-dihydropyrazine, 2,3,5,6-tetramethyl 1,4-bis (tri-n-propylsilyl) -1,4-dihydropyrazine, 2, 3,5,6-tetramethyl 1,4-bis (triisopropylsilyl) -1,4-dihydropyrazine, 1,4-bis (tri-n-butylsilyl) -1,4-dihydropyrazine, 2,3,5 , 6-Tetramethyl 1,4-bis (triisobutylsilyl) -1,4-dihydropyrazine, 2,3,5,6-tetramethyl 1,4-bis (trisec-butylsilyl) -1,4-dihydro Pyrazine, 2,3,5,6-tetramethyl 1,4-bis (tritert-butylsilyl) -1,4-dihydropyrazine, 2,3,5,6-tetraethyl 1,4-bis (trimethyl) Ryl) -1,4-dihydropyrazine, 2,3,5,6-tetraethyl 1,4-bis (triethylsilyl) -1,4-dihydropyrazine, 2,3,5,6-tetraethyl 1,4-bis (Tri-n-propylsilyl) -1,4-dihydropyrazine, 2,3,5,6-tetraethyl 1,4-bis (triisopropylsilyl) -1,4-dihydropyrazine, 2,3,5,6- Tetraethyl 1,4-bis (tri-n-butylsilyl) -1,4-dihydropyrazine, 2,3,5,6-tetraethyl 1,4-bis (triisobutylsilyl) -1,4-dihydropyrazine, 2,3 , 5,6-tetraethyl 1,4-bis (trisec-butylsilyl) -1,4-dihydropyrazine, 2,3,5,6-tetraethyl 1,4-bis (tri tert-butylsilyl) ) -1,4-dihydropyrazine, 2,3,5,6-tetra n-propyl 1,4-bis (trimethylsilyl) -1,4-dihydropyrazine, 2,3,5,6-tetraisopropyl 1, 4-bis (trimethylsilyl) -1,4-dihydropyrazine, 2,3,5,6-tetra n-butyl 1,4-bis (tri-n-propylsilyl) -1,4-dihydropyrazine, 2,3, 5,6-tetrasec-butyl 1,4-bis (trimethylsilyl) -1,4-dihydropyrazine, 2,3,5,6-tetratert-butyl 1,4-bis (trimethylsilyl) -1,4-dihydro Pyrazine, 3,6-bis (trimethylsilyl) cyclohexane-1,4-diene (BTCD), (2-methylcyclohexa-2,5-diene-1,4-diyl) bis (trime And methine compounds such as (tilsilane) (MBTCD).
前記一般式で示される化合物は、例えば下記一般式
（前記式中、Ｘ１およびＸ２はそれぞれ同一であるか又は異なって窒素原子あるいはメチン基であり、Ｒ３、Ｒ４、Ｒ５およびＲ６はそれぞれ同一であるか又は異なって水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基又はｔｅｒｔ−ブチル基である。）
で示される原料のジヒドロピラジン化合物と、一般式ＨＳｉＹ３（但し、Ｙは水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基又はｔｅｒｔ−ブチル基である。）で示されるケイ素化合物を触媒の存在下又は不存在下に反応させることによって得ることができる。
(In the above formula, X 1 and X 2 are the same or different and each is a nitrogen atom or a methine group; R 3 , R 4 , R 5 and R 6 are the same or different and each represents a hydrogen atom; (Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group or tert-butyl group.)
And a dihydropyrazine compound of the general formula HSiY 3 (wherein Y is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group or tert-butyl group) -Butyl group) can be obtained by reacting in the presence or absence of a catalyst.
前記原料のジヒドロピラジン化合物としては、１，４−ジヒドロピラジン、２，３，５，６−テトラメチル −１，４−ジヒドロピラジン、２，３，５，６−テトラエチル−１，４−ジヒドロピラジン、２，３，５，６−テトラｎ−プロピル−１，４−ジヒドロピラジン、２，３，５，６−テトライソプロピル−１，４−ジヒドロピラジン、２，３，５，６−テトラｎ−ブチル−１，４−ジヒドロピラジン、２，３，５，６−テトラｓｅｃ−ブチル−１，４−ジヒドロピラジン、２，３，５，６−テトラｔｅｒｔ−ブチル−１，４−ジヒドロピラジなどが挙げられる。 Examples of the raw material dihydropyrazine compound include 1,4-dihydropyrazine, 2,3,5,6-tetramethyl-1,4-dihydropyrazine, 2,3,5,6-tetraethyl-1,4-dihydropyrazine. 2,3,5,6-tetran-propyl-1,4-dihydropyrazine, 2,3,5,6-tetraisopropyl-1,4-dihydropyrazine, 2,3,5,6-tetran- Examples include butyl-1,4-dihydropyrazine, 2,3,5,6-tetrasec-butyl-1,4-dihydropyrazine, 2,3,5,6-tetratert-butyl-1,4-dihydropyrazine, and the like. It is done.
前記の触媒としては、白金、固体担体に支持された白金、塩化白金酸、塩化白金酸と、アルコール、アルデヒド又はケトンとの錯体、白金−オレフィン錯体、白金−ビニルシロキサン錯体、白金−フォスフィン錯体、白金−フォスファイト錯体、ジカルボニルジクロロ白金、白金−炭化水素錯体、白金−アルコラート触媒など、一般式Ａ+〔ＨＭｍＸｎ〕-（式中、Ａ+はアルカリ金属カチオン、アンモニウムカチオン又はホスホニウムカチオンで、Ｍは金属、例えばＣｒ、Ｍｏ又はＷで、Ｘは極性基、例えばＣＯであり、ｍ、ｎは整数で、例えばｍ＝２、ｎ＝１０である。）で表される錯体、例えば前記カチオンがテトラメチルアンモニウムカチオン、テトラエチルアンモニウムカチオン、テトラブチルアンモニウムカチオン、ベンジルトリメチルアンモニウムカチオン、セチルトリメチルアンモニウムカチオンなどの四級アンモニウムカチオン、テトラフェニルホスホニウムカチオンなどの四級ホスホニウムカチオンである錯体が挙げられる。 Examples of the catalyst include platinum, platinum supported on a solid support, chloroplatinic acid, a complex of chloroplatinic acid and an alcohol, an aldehyde or a ketone, a platinum-olefin complex, a platinum-vinylsiloxane complex, a platinum-phosphine complex, Platinum-phosphite complex, dicarbonyldichloroplatinum, platinum-hydrocarbon complex, platinum-alcolate catalyst, etc. General formula A + [HM m X n ] - (where A + is an alkali metal cation, ammonium cation or phosphonium cation) M is a metal such as Cr, Mo or W, X is a polar group such as CO, m and n are integers such as m = 2 and n = 10), for example, The cation is tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, benzyl Trimethyl ammonium cation, quaternary ammonium cations, such as cetyl trimethyl ammonium cation, include complexes quaternary phosphonium cations such as tetraphenylphosphonium cation.
前記の反応は無溶媒で行ってもよくあるいは溶媒中で行ってもよい。前記溶媒としては、エチルエーテル、テトラヒドロフラン（ＴＨＦ）、ジメトキシエタン（ＤＭＥ）、ジオキサン、ピリジン等の極性溶媒が挙げられる。
また、前記の反応は０〜１５０℃の範囲、例えば５０〜１５０℃で実施し得る。
The above reaction may be carried out without solvent or in a solvent. Examples of the solvent include polar solvents such as ethyl ether, tetrahydrofuran (THF), dimethoxyethane (DME), dioxane, and pyridine.
Moreover, the said reaction may be implemented in the range of 0-150 degreeC, for example, 50-150 degreeC.
また、前記のメチン系化合物はベンゼン、トルエンを出発原料として合成し得る。
例えば、アルゴン雰囲気下、ＴＨＦ（１００ｍＬ）中に塩化トリメチルシランの所定量、典型的には４０．２ｍＬとリチウム片所定量、典型的には２．２０ｇとを加えて低温、典型的には５℃で撹拌を行って、ここにベンゼン又はトルエン、典型的には１６．７ｍＬのベンゼン又はトルエンをゆっくりと滴下し、長時間、典型的には１週間、低温、典型的には５℃で撹拌を行った後、上澄み液を分離・濃縮を行って、得られた残渣を減圧蒸留により精製して得ることができる。
The methine compounds can be synthesized using benzene and toluene as starting materials.
For example, a predetermined amount of trimethylsilane chloride, typically 40.2 mL, and a predetermined amount of lithium strip, typically 2.20 g, are added to THF (100 mL) under an argon atmosphere at a low temperature, typically 5 Stir at ℃, then slowly add benzene or toluene, typically 16.7 mL benzene or toluene, and stir for a long time, typically 1 week, at low temperature, typically 5 ° C. Then, the supernatant is separated and concentrated, and the resulting residue can be purified by distillation under reduced pressure.
本発明の前記一般式で示される化合物からなる還元剤は任意の還元反応に用い得るが、好適には金属イオンの還元に用い得る。
本発明の実施態様においては、本発明の還元剤を用いることによって、溶媒中で金属イオンを還元し得る。
The reducing agent comprising the compound represented by the general formula of the present invention can be used for any reduction reaction, but can be preferably used for reduction of metal ions.
In an embodiment of the present invention, metal ions can be reduced in a solvent by using the reducing agent of the present invention.
前記一般式で示される化合物を還元剤として適用し得る金属イオンとしては、様々な金属イオン、例えばＦｅ２＋（−０．４４０Ｖ）、Ｃｏ２＋（−０．２７７Ｖ）、Ｎｉ２＋（−０．２５Ｖ）、Ｃｕ２＋（０．３３７Ｖ）、Ｇａ３＋（−０．５２９Ｖ）、Ｒｈ３＋（０．７５８Ｖ）、Ｐｄ２＋（０．９１５Ｖ）、Ａｇ＋（０．７９９Ｖ）、Ｐｔ２＋（１．１９Ｖ）、Ａｕ３＋（１．５２Ｖ）などが挙げられる［括弧内の数値は金属イオンの標準酸化還元電位（Ｖ）を示す。］。
これらの金属イオンは、溶媒中、本発明の還元剤と接触させることにより金属を生成し得る。金属イオンの還元反応は金属イオンが１種の場合に限定されず、少なくとも２種の金属イオン、例えばＧａイオンとＧａイオンよりも高い標準酸化還元電位を有する少なくとも１種の金属イオンとを組み合わせて合金を形成し得る。
Examples of metal ions to which the compound represented by the general formula can be applied as a reducing agent include various metal ions such as Fe 2+ (−0.440 V), Co 2+ (−0.277 V), Ni 2+ (−0.25 V). ), Cu 2+ (0.337 V), Ga 3+ (−0.529 V), Rh 3+ (0.758 V), Pd 2+ (0.915 V), Ag + (0.799 V), Pt 2+ (1.19 V) , Au 3+ (1.52 V), etc. [The numerical values in parentheses indicate the standard oxidation-reduction potential (V) of metal ions. ].
These metal ions can produce a metal by contacting with the reducing agent of the present invention in a solvent. The reduction reaction of metal ions is not limited to the case where there is only one metal ion, but a combination of at least two metal ions, for example, Ga ions and at least one metal ion having a standard oxidation-reduction potential higher than Ga ions. Alloys can be formed.
本発明の実施態様の金属の製造方法は、少なくとも１種の金属イオン源となるそれぞれの金属錯体と、本発明の還元剤とを、溶媒、例えばエチルエーテル、テトラヒドロフラン（ＴＨＦ）、ジメトキシエタン（ＤＭＥ）、ジオキサン、ピリジン等の極性溶媒に溶解又は懸濁させて実施され得る。そのため、金属のイオン源となる金属錯体としては、溶媒に可溶性の種々の金属錯体が好適である。 In the method for producing a metal according to an embodiment of the present invention, each metal complex serving as at least one metal ion source and the reducing agent of the present invention are mixed with a solvent such as ethyl ether, tetrahydrofuran (THF), dimethoxyethane (DME). ), Dioxane, pyridine or the like in a polar solvent. Therefore, various metal complexes that are soluble in a solvent are suitable as a metal complex that serves as a metal ion source.
前記金属イオン源として好適な金属錯体としては、例えば前記金属イオンの塩化物、硝酸塩、硫酸塩、カルボン酸塩等、具体例として、例えば、塩化鉄（ＩＩ）（ＦｅＣｌ２）、銅の場合は塩化銅（ＩＩ）（ＣｕＣｌ２）、塩化銅（II）テトラヒドロフラン錯体、硝酸銅（ＩＩ）（Ｃｕ（ＮＯ３）２）、硫酸銅（ＩＩ）五水和物（ＣｕＳＯ４・５Ｈ２Ｏ）、ピバル酸銅（ＩＩ）（Ｃｕ（ＯＣＯｔＢｕ）２）等、塩化銀（Ｉ）（ＡｇＣｌ）、硝酸銀（Ｉ）（ＡｇＮＯ３）、メタンスルホン酸銀（ＣＨ３ＳＯ３Ａｇ）、トリフルオロメタンスルホン酸銀（ＣＦ３ＳＯ３Ａｇ）、硝酸パラジウム（ＩＩ）（Ｐｄ（ＮＯ２）２／Ｈ２Ｏ）や塩化パラジウム（ＩＩ）（ＰｄＣｌ２）、塩化ガリウム（ＩＩＩ）（（ＧａＣｌ３）、金の場合はテトラクロロ金（ＩＩＩ）酸四水和物（ＨＡｕＣｌ４・４Ｈ２Ｏ）、ジニトロジアンミン白金（ＩＩ）（Ｐｔ（ＮＯ２）２（ＮＨ３）２）やヘキサクロロ白金（ＩＶ）酸六水和物（Ｈ２（ＰｔＣｌ６）・６Ｈ２Ｏ）、塩化ロジウム（ＩＩＩ）（ＲｈＣｌ３・３Ｈ２Ｏ）などが挙げられる。 Examples of metal complexes suitable as the metal ion source include chlorides, nitrates, sulfates, carboxylates, and the like of the metal ions. Specific examples include, for example, iron (II) chloride (FeCl 2 ) and copper. Copper (II) chloride (CuCl 2 ), copper (II) chloride tetrahydrofuran complex, copper (II) nitrate (Cu (NO 3 ) 2 ), copper (II) sulfate pentahydrate (CuSO 4 .5H 2 O), Copper (II) pivalate (Cu (OCO t Bu) 2 ), silver chloride (I) (AgCl), silver nitrate (I) (AgNO 3 ), silver methanesulfonate (CH 3 SO 3 Ag), trifluoromethanesulfone Silver oxide (CF 3 SO 3 Ag), palladium nitrate (II) (Pd (NO 2 ) 2 / H 2 O), palladium chloride (II) (PdCl 2 ), gallium chloride (III) ((GaCl 3 ), For gold tetrachloroaurate (III) acid tetrahydrate (HAuCl 4 · 4H 2 O) , dinitro diammine platinum (II) (Pt (NO 2 ) 2 (NH 3) 2) and hexachloroplatinic (IV) acid Examples thereof include hexahydrate (H 2 (PtCl 6 ) · 6H 2 O), rhodium (III) chloride (RhCl 3 · 3H 2 O), and the like.
本発明の実施態様において、溶媒中の前記還元剤の濃度は特に限定されないが、還元剤の濃度が低いほど、金属イオンの還元、析出速度を遅くして、形成される個々の金属微粒子の一次粒子（例えばナノ粒子）径を小さくできる傾向があることから、金属粒子を得ようとする場合は目的とする一次粒子径の範囲等に応じて、好適な濃度の範囲を設定するのが好ましい。例えば、前記還元剤の金属錯体に対する割合（モル比）は、好適には０．１：１〜１０：１の範囲、例えば０．５：１〜２：１の範囲、典型的には１：１である。
本発明の実施態様において、溶媒中で本発明の還元剤を用いることによって、任意の温度、好適には室温で還元反応を実施して金属、例えば金属ナノ粒子又は金属薄膜を製造し得る。
In the embodiment of the present invention, the concentration of the reducing agent in the solvent is not particularly limited. However, the lower the concentration of the reducing agent, the slower the reduction and deposition rate of the metal ions, and the primary metal fine particles formed. Since there is a tendency to reduce the particle (for example, nanoparticle) diameter, it is preferable to set a suitable concentration range according to the intended primary particle diameter range or the like when obtaining metal particles. For example, the ratio of the reducing agent to the metal complex (molar ratio) is preferably in the range of 0.1: 1 to 10: 1, such as in the range of 0.5: 1 to 2: 1, typically 1: 1.
In an embodiment of the present invention, by using the reducing agent of the present invention in a solvent, a reduction reaction can be carried out at any temperature, preferably at room temperature, to produce a metal, such as a metal nanoparticle or a metal thin film.
本発明の実施態様において前記一般式で示される化合物を還元剤として用いることにより、金属イオン源から金属、例えば金属ナノ粒子を製造し得る理論的な解明は十分にはなされていないが、図１に示すように、一例として金属イオン源としてＭＣｌ２を用いると、先ず還元剤として用いる前記一般式で示される化合物（前記式中、Ｘ１、Ｘ２は窒素原子、Ｒ１およびＲ２はメチル基）が電子の豊富なジエン配位子として金属イオン源に配位する。配位によって還元剤の窒素−ケイ素結合が伸長し、金属イオン源に結合していた配位子（例えば塩素配位子）と交換反応が進行して金属−窒素結合を持つ錯体が形成される。次に、金属−窒素結合が均一開裂を起こすことで、金属の還元反応が進行する。この際、生成したラジカル性の有機物は再度、金属イオン源と反応し、最終的に複素芳香族化合物と金属還元種を与える。本発明の実施態様における還元剤の特長は、ジエン配位子として金属中心に配位した後に、分子内反応として還元反応が進行する点であり、還元剤自体の標準酸化還元電位よりさらに負の標準酸化還元電位を持つ金属イオンの金属イオン源の還元が可能となることである。 In the embodiment of the present invention, the theoretical elucidation that a metal, for example, a metal nanoparticle can be produced from a metal ion source by using the compound represented by the above general formula as a reducing agent has not been sufficiently made. As shown in FIG. 1, when MCl 2 is used as a metal ion source as an example, a compound represented by the above general formula used as a reducing agent (wherein X 1 and X 2 are nitrogen atoms, R 1 and R 2 are methyl Group) coordinates to the metal ion source as a diene ligand rich in electrons. Coordination extends the nitrogen-silicon bond of the reducing agent, and the exchange reaction proceeds with a ligand (for example, a chlorine ligand) that has been bound to the metal ion source to form a complex having a metal-nitrogen bond. . Next, the metal-nitrogen bond undergoes uniform cleavage, whereby the metal reduction reaction proceeds. At this time, the generated radical organic substance reacts with the metal ion source again, and finally gives a heteroaromatic compound and a metal reducing species. The feature of the reducing agent in the embodiment of the present invention is that the reduction reaction proceeds as an intramolecular reaction after coordination to the metal center as a diene ligand, which is more negative than the standard redox potential of the reducing agent itself. It is possible to reduce a metal ion source of a metal ion having a standard redox potential.
本発明の実施態様によれば、本発明の還元剤と種々の金属イオン源を溶媒中で接触させて金属、例えば金属ナノ粒子又は金属薄膜を生成し得る。 According to an embodiment of the present invention, the reducing agent of the present invention and various metal ion sources can be contacted in a solvent to produce a metal, such as a metal nanoparticle or a metal thin film.
以下、本発明の実施例を示す。
以下の実施例は単に説明するためのものであり、本発明を限定するものではない。
Examples of the present invention will be described below.
The following examples are for illustrative purposes only and are not intended to limit the invention.
参考例１
Ｍｅ４ＢＴＤＰの合成
アルゴン雰囲気下、テトラヒドロフラン６０ｍＬを溶媒とし、２，３，５，６−テトラメチルピラジン５．０９ｇ（３７．４ｍｍｏｌ）とクロロトリメチルシラン１４．３ｍＬ（１１２．３ｍｍｏｌ）を０．５〜１．０ｃｍ角に切断した金属カリウム片（４．３９ｇ、１１２．３ｍｍｏｌ）存在下で混合した。常温で４８時間撹拌後、反応溶液の上澄み液を分取・濃縮し、得られた淡青色固体を減圧条件下で昇華精製を行うことで、７．４１ｇの白色粉末を得た（収率７１％）。
得られた生成物の１Ｈ ＮＭＲスペクトルから化学式Ｃ１４Ｈ３０Ｎ２Ｓｉ２で示される２，３，５，６−テトラメチル １，４−ビス（トリメチルシリル）−１，４−ジヒドロピラジン（以下、Ｍｅ４ＢＴＤＰと略記する場合もある。）であることが確認された。
１Ｈ ＮＭＲスペクトルの測定結果
１Ｈ ＮＭＲ（４００ ＭＨｚ、ｄ８−ＴＨＦ）：δ１．７１（ｓ、１２Ｈ、Ｍｅ４ＢＴＤＰのＭｅ）、０．２０（ｓ、１８Ｈ、Ｍｅ４ＢＴＤＰのＭｅ）
Reference example 1
Synthesis of Me 4 BTDP Under an argon atmosphere, tetrahydrofuran (60 mL) was used as a solvent, and 2,3,5,6-tetramethylpyrazine (5.09 g, 37.4 mmol) and chlorotrimethylsilane (14.3 mL, 112.3 mmol) were added to 0.5. It mixed in presence of the metal potassium piece (4.39g, 112.3mmol) cut | disconnected to the -1.0cm square. After stirring at room temperature for 48 hours, the supernatant of the reaction solution was collected and concentrated, and the resulting light blue solid was purified by sublimation under reduced pressure to obtain 7.41 g of a white powder (yield 71). %).
From the 1H NMR spectrum of the resulting product, 2,3,5,6-tetramethyl 1,4-bis (trimethylsilyl) -1,4-dihydropyrazine (hereinafter referred to as the chemical formula C 14 H 30 N 2 Si 2 ) It may be abbreviated as Me 4 BTDP).
Measurement result of 1 H NMR spectrum 1H NMR (400 MHz, d 8 -THF): δ 1.71 (s, 12H, Me 4 BTDP Me), 0.20 (s, 18H, Me 4 BTDP Me)
実施例１
室温で、Ｊ−ｙｏｕｎｇ型ＮＭＲ管中、１９ｍｇ（０．１０ｍｍｏｌ）の塩化銅（II）テトラヒドロフラン錯体（ＣｕＣｌ２（ｔｈｆ）０．８）のｄ８−ＴＨＦ（０．５０ｍＬ）懸濁液（図２（ａ））に対して５７ｍｇ（０．２０ｍｍｏｌ）のＭｅ４ＢＴＤＰを加えた。反応液はすぐに赤銅色の懸濁液に変化した（図２（ｂ））。ＮＭＲ測定結果から、０．１０ｍｍｏｌのＭｅ４ＢＴＤＰの消費と、０．１０ｍｍｏｌのテトラメチルピラジン（Ｍｅ４ｐｙｒａｚｉｎｅ）および０．２０ｍｍｏｌの塩化トリメチルシラン（ＴＭＳＣｌ）の生成、従って２電子還元の進行が確認された（図３）。
１Ｈ ＮＭＲスペクトルの測定結果
１Ｈ ＮＭＲ（４００ ＭＨｚ、ｄ８−ＴＨＦ）：δ２．４１（ｓ、１２Ｈ、Ｍｅ４ｐｙｒａｚｉｎｅのＭｅ）、１．７１（ｓ、１２Ｈ、Ｍｅ４ＢＴＤＰのＭｅ）、０．４５（ｓ、１８Ｈ、ＴＭＳＣｌ）、０．２０（ｓ、１８Ｈ、Ｍｅ４ＢＴＤＰのＴＭＳ）
Example 1
At room temperature, a suspension of d 8 -THF (0.50 mL) of 19 mg (0.10 mmol) of copper (II) chloride tetrahydrofuran complex (CuCl 2 (thf) 0.8 ) in a J-young type NMR tube (Fig. 2 (a)) was added 57 mg (0.20 mmol) of Me 4 BTDP. The reaction liquid immediately changed to a bronze suspension (FIG. 2 (b)). From the NMR measurement results, it was confirmed that 0.10 mmol of Me 4 BTDP was consumed and 0.10 mmol of tetramethylpyrazine (Me 4 pyrazine) and 0.20 mmol of trimethylsilane chloride (TMSCl) were formed, and thus the progress of two-electron reduction was confirmed. (FIG. 3).
Measurement result of 1 H NMR spectrum 1H NMR (400 MHz, d 8 -THF): δ 2.41 (Me of s, 12H, Me 4 pyrazine), 1.71 (Me of s, 12H, Me 4 BTDP), 0 .45 (s, 18H, TMSCl), 0.20 (s, 18H, TMS of Me 4 BTDP)
実施例２
シュレンク管中、アルゴン雰囲気下で調製した、黄色の塩化銅（II）ＴＨＦ錯体（ＣｕＣｌ２（ｔｈｆ）０．８）９６ｍｇ（０．５０ｍｍｏｌ）のＴＨＦ懸濁液（５．０ｍＬ）に対し、Ｍｅ４ＢＴＤＰ１４１ｍｇ（０．５０ｍｍｏｌ）のＴＨＦ溶液（５．０ｍＬ）を室温で滴下した。滴下後すぐに反応混合物の色が黄色から焦げ茶色へと変化した（還元剤Ｍｅ４ＢＴＤＰ添加前：図４（ａ）、Ｍｅ４ＢＴＤＰ添加直後：図４（ｂ））。３０分後、撹拌を止めて静置して固体を沈降させた（Ｍｅ４ＢＴＤＰ添加して３０分後：図４（ｃ））。上澄み液を濾別した後、得られた沈殿を５．０ｍＬのＴＨＦで３回洗浄した。洗浄後の固体を乾燥させ、３０ｍｇの銅粉末（０．４７ｍｍｏｌ、収率９５％）を得た。
Example 2
In a Schlenk tube prepared under an argon atmosphere, a suspension of yellow copper (II) THF complex (CuCl 2 (thf) 0.8 ) 96 mg (0.50 mmol) in THF (5.0 mL) was dissolved in Me. 4 A THF solution (5.0 mL) of BTDP 141 mg (0.50 mmol) was added dropwise at room temperature. Immediately after the dropwise addition, the color of the reaction mixture changed from yellow to dark brown (before addition of the reducing agent Me 4 BTDP: FIG. 4 (a), immediately after Me 4 BTDP addition: FIG. 4 (b)). After 30 minutes, stirring was stopped and the mixture was allowed to stand to precipitate the solid (30 minutes after adding Me 4 BTDP: FIG. 4 (c)). After the supernatant was filtered off, the resulting precipitate was washed 3 times with 5.0 mL of THF. The washed solid was dried to obtain 30 mg of copper powder (0.47 mmol, yield 95%).
実施例３
シュレンク管中、アルゴン雰囲気下で調製した、青色のピバル酸銅（II）９６ｍｇ（０．５０ｍｍｏｌ）のＴＨＦ溶液（５．０ｍＬ）に対し、Ｍｅ４ＢＴＤＰ１４１ｍｇ（０．５０ｍｍｏｌ）のＴＨＦ溶液（５．０ｍＬ）を室温で滴下した。滴下後徐々に反応溶液の色が黄緑色へと変化した（図５（ｂ）、図５（ｃ））。さらに撹拌を続けると、反応液は徐々に赤茶色（図５（ｄ））、さらに黒褐色（図５（ｅ））へ変化した。シュレンク管内でこの溶液から４８時間後に銅鏡が生成していることが確認された（還元剤Ｍｅ４ＢＴＤＰ添加前：図５（ａ）、Ｍｅ４ＢＴＤＰ添加直後：図５（ｂ）、Ｍｅ４ＢＴＤＰ添加して１５分後：図５（ｃ）、Ｍｅ４ＢＴＤＰ添加して９０分後：図５（ｄ）、Ｍｅ４ＢＴＤＰ添加して１３時間後：図５（ｅ））。
Example 3
Schlenk, was prepared under argon, to a THF solution (5.0 mL) of blue pivalic copper (II) 96mg (0.50mmol), Me 4 THF solution (5 BTDP141mg (0.50mmol). 0 mL) was added dropwise at room temperature. After the dropwise addition, the color of the reaction solution gradually changed to yellowish green (FIGS. 5B and 5C). When stirring was further continued, the reaction solution gradually changed to reddish brown (FIG. 5 (d)) and further to blackish brown (FIG. 5 (e)). It was confirmed that a copper mirror was formed after 48 hours from this solution in the Schlenk tube (before addition of the reducing agent Me 4 BTDP: FIG. 5 (a), immediately after the addition of Me 4 BTDP: FIG. 5 (b), Me 4 BTDP. 15 minutes after the addition: FIG. 5 (c), 90 minutes after the addition of Me 4 BTDP: FIG. 5 (d), 13 hours after the addition of Me 4 BTDP: FIG. 5 (e)).
実施例４
シュレンク管中、アルゴン雰囲気下で調製した、白色の塩化銀（I）７２ｍｇ（０．５０ｍｍｏｌ）のＴＨＦ懸濁液（５．０ｍＬ）に対し、Ｍｅ４ＢＴＤＰ７１ｍｇ（０．２５ｍｍｏｌ）のＴＨＦ溶液（５．０ｍＬ）を遮光条件下、室温で滴下した。１８時間後、撹拌を止めて静置し、固体を沈降させた。上澄み液を濾別した後、得られた沈殿を５．０ｍＬのＴＨＦで３回洗浄した。洗浄後の固体を乾燥させ、４８ｍｇの銀粉末（０．４５ｍｍｏｌ、収率９０％）を得た。
Example 4
To a THF suspension (5.0 mL) of white silver chloride (I) 72 mg (0.50 mmol) prepared in a Schlenk tube under an argon atmosphere, Me 4 BTDP 71 mg (0.25 mmol) in a THF solution (5 0.0 mL) was added dropwise at room temperature under light-shielding conditions. After 18 hours, stirring was stopped and the mixture was allowed to stand to allow the solid to settle. After the supernatant was filtered off, the resulting precipitate was washed 3 times with 5.0 mL of THF. The washed solid was dried to obtain 48 mg of silver powder (0.45 mmol, yield 90%).
実施例５
シュレンク管中、アルゴン雰囲気下で調製した、黄土色の塩化鉄（II）６３ｍｇ（０．５０ｍｍｏｌ）のＴＨＦ懸濁液（５．０ｍＬ）に対し、Ｍｅ４ＢＴＤＰ１４１ｍｇ（０．５０ｍｍｏｌ）のＴＨＦ溶液（５．０ｍＬ）を室温で滴下した。撹拌後すぐに反応溶液は黒色になった。６時間後、撹拌を止めて静置し、固体を沈降させた。上澄み液を濾別した後、得られた沈殿を５．０ｍＬのＴＨＦで３回洗浄した。洗浄後の固体を乾燥させ、２８ｍｇの鉄粉末（０．５０ｍｍｏｌ、収率１００％）を得た。
Example 5
To a THF suspension (5.0 mL) of 63 mg (0.50 mmol) of ocherous iron (II) chloride prepared in a Schlenk tube under an argon atmosphere, a THF solution of 141 mg (0.50 mmol) of Me 4 BTDP ( 5.0 mL) was added dropwise at room temperature. Immediately after stirring, the reaction solution turned black. After 6 hours, stirring was stopped and the mixture was allowed to stand to precipitate the solid. After the supernatant was filtered off, the resulting precipitate was washed 3 times with 5.0 mL of THF. The washed solid was dried to obtain 28 mg of iron powder (0.50 mmol, yield 100%).
実施例６
シュレンク管中、アルゴン雰囲気下で調製した、茶色の塩化パラジウム（II）８９ｍｇ（０．５０ｍｍｏｌ）のＴＨＦ懸濁液（５．０ｍＬ）に対し、Ｍｅ４ＢＴＤＰ１４１ｍｇ（０．５０ｍｍｏｌ）のＴＨＦ溶液（５．０ｍＬ）を室温で滴下した。速やかに黒色の懸濁液となった。１２時間後、撹拌を止めて静置し、黒色固体を沈降させた。褐色の上澄み液を濾別した後、得られた沈殿を５．０ｍＬのＴＨＦで３回洗浄した。洗浄後の固体を乾燥させ、２７ｍｇの黒色のパラジウム粉末（０．２５ｍｍｏｌ、収率５０％）を得た。
Example 6
To a THF suspension (5.0 mL) of 89 mg (0.50 mmol) of brown palladium (II) chloride prepared in a Schlenk tube under an argon atmosphere, 141 mg (0.50 mmol) of a THF solution of Me 4 BTDP (0.50 mmol) 0.0 mL) was added dropwise at room temperature. A black suspension was immediately obtained. After 12 hours, stirring was stopped and the mixture was allowed to stand to precipitate a black solid. After filtering off the brown supernatant, the resulting precipitate was washed three times with 5.0 mL of THF. The washed solid was dried to obtain 27 mg of black palladium powder (0.25 mmol, yield 50%).
実施例７
室温で、Ｊ−ｙｏｕｎｇ型ＮＭＲ管中、１８ｍｇ（０．１０ｍｍｏｌ）の塩化ガリウムのｄ８−ＴＨＦ（０．５０ｍＬ）溶液に対して、５７ｍｇ（０．２０ｍｍｏｌ）のＭｅ４ＢＴＤＰを加えた。反応液はすぐに黄灰色の懸濁液に変化した。ＮＭＲ測定の結果から、０．１５ｍｍｏｌのＭｅ４ＢＴＤＰの消費と、０．１５ｍｍｏｌのテトラメチルピラジンおよび０．３０ｍｍｏｌの塩化トリメチルシランの生成が確認され、３電子還元の進行が確認された（図６）。
１Ｈ ＮＭＲスペクトルの測定結果
１Ｈ ＮＭＲ（４００ ＭＨｚ、ｄ８−ＴＨＦ）：δ２．４１（ｓ、１２Ｈ、Ｍｅ４ｐｙｒａｚｉｎｅのＭｅ）、１．７１（ｓ、１２Ｈ、Ｍｅ４ＢＴＤＰのＭｅ）、０．４５（ｓ、１８Ｈ、ＴＭＳＣｌ）、０．２０（ｓ、１８Ｈ、Ｍｅ４ＢＴＤＰのＭｅ）
Example 7
At room temperature, 57 mg (0.20 mmol) of Me 4 BTDP was added to a solution of 18 mg (0.10 mmol) of gallium chloride in d 8 -THF (0.50 mL) in a J-young type NMR tube. The reaction immediately changed to a yellow-gray suspension. As a result of NMR measurement, consumption of 0.15 mmol of Me 4 BTDP and generation of 0.15 mmol of tetramethylpyrazine and 0.30 mmol of trimethylsilane chloride were confirmed, confirming the progress of 3-electron reduction (FIG. 6). ).
Measurement result of 1 H NMR spectrum 1H NMR (400 MHz, d 8 -THF): δ 2.41 (Me of s, 12H, Me 4 pyrazine), 1.71 (Me of s, 12H, Me4BTDP), 0.45 (S, 18H, TMSCl), 0.20 (s, 18H, Me 4 BTDP Me)
実施例８
シュレンク管中、アルゴン雰囲気下で調製した、無色の塩化ガリウム（II）８８ｍｇ（０．５０ｍｍｏｌ）のＴＨＦ懸濁液（１０ｍＬ）に対し、Ｍｅ４ＢＴＤＰ２１２ｍｇ（０．７５ｍｍｏｌ）のＴＨＦ溶液（１０ｍＬ）を室温で滴下した。滴下後すぐに灰色の懸濁液となった。１５時間後、撹拌を止めて静置し、固体を沈降させた。黄色で粘性の高い上澄み液を濾別した後、得られた沈殿を５．０ｍＬのＴＨＦで３回洗浄した。洗浄後の固体を乾燥させ、２０ｍｇの灰色のガリウム粉末（０．２９ｍｍｏｌ、収率５９％）を得た。
Example 8
To a THF suspension (10 mL) of colorless gallium chloride (II) 88 mg (0.50 mmol) prepared in a Schlenk tube under an argon atmosphere, a THF solution (10 mL) of Me 4 BTDP 212 mg (0.75 mmol) was added. Added dropwise at room temperature. Immediately after the addition, a gray suspension was formed. After 15 hours, stirring was stopped and the mixture was allowed to stand to allow the solid to settle. After filtering off the yellow and highly viscous supernatant, the resulting precipitate was washed three times with 5.0 mL of THF. The washed solid was dried to obtain 20 mg of gray gallium powder (0.29 mmol, yield 59%).
実施例９
シュレンク管中、アルゴン雰囲気下で調製したトリフルオロメタンスルホン酸銀（I）（化学式：ＣＦ３ＳＯ３Ａｇ）（ＡｇＯＴｆと略記する場合もある。）５．１ｍｇ（０．０２ｍｍｏｌ）のピリジン溶液（２．５ｍＬ）に対し、Ｍｅ４ＢＴＤＰ２．８ｍｇ（０．０１ｍｍｏｌ）のピリジン溶液（２．５ｍＬ）を室温で滴下した。１時間後、撹拌を止めて静置し、銀ナノ粒子分散液を得た。得られた分散液をＳＴＥＭ分析用グリッドに滴下させ、乾燥した後にＳＴＥＭ観察を行ったＥＤＸによるナノ粒子の組成分析を行った結果、生成した粒子が銀粒子であることを確認した。
Ａｇナノ粒子のＳＴＥＭ観察結果を図７に、ＥＤＸスペクトルを図８に示す。
Example 9
Silver (I) trifluoromethanesulfonate (chemical formula: CF 3 SO 3 Ag) (sometimes abbreviated as AgOTf) prepared in a Schlenk tube under an argon atmosphere 5.1 mg (0.02 mmol) of a pyridine solution (2 0.5 mL), a pyridine solution (2.5 mL) of Me 4 BTDP 2.8 mg (0.01 mmol) was added dropwise at room temperature. After 1 hour, stirring was stopped and the mixture was allowed to stand to obtain a silver nanoparticle dispersion. The obtained dispersion was dropped on a grid for STEM analysis, dried, and then subjected to STEM observation to analyze the composition of nanoparticles by EDX. As a result, it was confirmed that the generated particles were silver particles.
The STEM observation results of the Ag nanoparticles are shown in FIG. 7, and the EDX spectrum is shown in FIG.
実施例１０
シュレンク管中、アルゴン雰囲気下で調製した塩化銅ＴＨＦ錯体（II）１５．４ｍｇ（０．０８ｍｍｏｌ）のピリジン溶液（１０ｍＬ）に対し、Ｍｅ４ＢＴＤＰ２２．６ｍｇ（０．０８ｍｍｏｌ）のピリジン溶液（１０ｍＬ）を室温で滴下した。１時間後、撹拌を止めて静置し、銅ナノ粒子分散液を得た。得られた分散液をＳＴＥＭ分析用グリッドに滴下させ、乾燥した後にＳＴＥＭ観察を行ったＥＤＸによるナノ粒子の組成分析を行った結果、生成した粒子が銅ナノ粒子であることを確認した。
Ｃｕナノ粒子のＳＴＥＭ観察結果を図９に、ＥＤＸスペクトルを図１０に示す。
Example 10
In a Schlenk tube, 15.4 mg (0.08 mmol) of a copper chloride THF complex (II) prepared in an argon atmosphere and a pyridine solution (10 mL), 22.6 mg of Me 4 BTDP (0.08 mmol) in a pyridine solution (10 mL) Was added dropwise at room temperature. After 1 hour, stirring was stopped and the mixture was allowed to stand to obtain a copper nanoparticle dispersion. The obtained dispersion was dropped on a grid for STEM analysis, dried, and then subjected to STEM observation to analyze the composition of nanoparticles by EDX. As a result, it was confirmed that the generated particles were copper nanoparticles.
The STEM observation results of the Cu nanoparticles are shown in FIG. 9, and the EDX spectrum is shown in FIG.
図２〜図１０から、本発明の還元剤の一例であるＭｅ４ＢＴＤＰと、標準酸化還元電位が−０．５２９Ｖ〜０．７９９Ｖの各種金属イオンの金属イオン源とを、室温で、溶媒中で接触させることによって金属ナノ粒子又は金属薄膜を生成させ得ることが確認された。 2 to 10, Me 4 BTDP, which is an example of the reducing agent of the present invention, and metal ion sources of various metal ions having a standard oxidation-reduction potential of −0.529 V to 0.799 V in a solvent at room temperature. It was confirmed that a metal nanoparticle or a metal thin film can be produced by contacting with.
本発明によって、溶媒中で金属イオンを還元し得る新規な還元剤を提供し得る。
また、本発明によって、溶媒中で前記還元剤を用いて金属を得ることができる。
According to the present invention, a novel reducing agent capable of reducing metal ions in a solvent can be provided.
Further, according to the present invention, a metal can be obtained using the reducing agent in a solvent.
Claims (8)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3781291A (en) * | 1971-05-26 | 1973-12-25 | R Sulzbach | Silylated 1,4-dihydropyridines |
| JP2006051489A (en) * | 2004-07-12 | 2006-02-23 | Sumitomo Chemical Co Ltd | Trimerization catalyst of olefin and trimerization method of olefin using this catalyst |
| JP2006232869A (en) * | 2005-02-22 | 2006-09-07 | Sumitomo Chemical Co Ltd | Olefin oligomerization catalyst and manufacturing method of olefin oligomer |
| JP2013184925A (en) * | 2012-03-08 | 2013-09-19 | Osaka Univ | Tungsten complex, catalyst for metathesis reaction and production method of cyclic olefin ring-opened polymer |
| WO2014210512A1 (en) * | 2013-06-28 | 2014-12-31 | Wayne State University | Bis(trimethylsilyl) six-membered ring systems and related compounds as reducing agents for forming layers on a substrate |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3781291A (en) * | 1971-05-26 | 1973-12-25 | R Sulzbach | Silylated 1,4-dihydropyridines |
| JP2006051489A (en) * | 2004-07-12 | 2006-02-23 | Sumitomo Chemical Co Ltd | Trimerization catalyst of olefin and trimerization method of olefin using this catalyst |
| JP2006232869A (en) * | 2005-02-22 | 2006-09-07 | Sumitomo Chemical Co Ltd | Olefin oligomerization catalyst and manufacturing method of olefin oligomer |
| JP2013184925A (en) * | 2012-03-08 | 2013-09-19 | Osaka Univ | Tungsten complex, catalyst for metathesis reaction and production method of cyclic olefin ring-opened polymer |
| WO2014210512A1 (en) * | 2013-06-28 | 2014-12-31 | Wayne State University | Bis(trimethylsilyl) six-membered ring systems and related compounds as reducing agents for forming layers on a substrate |
Non-Patent Citations (5)
| Title |
|---|
| ANGEWANDTE CHEMIE, vol. 96(8), JPN6017043560, 1984, pages 609 - 610 * |
| CHEMISCHE BERICHTE, vol. 128(8), JPN6017043555, 1995, pages 745 - 50 * |
| JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 105(4), JPN6017043558, 1983, pages 707 - 13 * |
| JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 136(13), JPN6017043554, 5 March 2014 (2014-03-05), pages 5161 - 5170 * |
| ORGANOSILICON CHEM., JPN6017043556, 1994, pages 41 - 42 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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