CN107236007A - 一种双核镍配合物及其制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000010668 complexation reaction Methods 0.000 title abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000010276 construction Methods 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 239000011591 potassium Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000036571 hydration Effects 0.000 claims description 14
- 238000006703 hydration reaction Methods 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- CXHLVSRLJAYJLY-UHFFFAOYSA-N O.[K].[N+](=O)([O-])C1=C(C(=O)O)NC(NC1=O)=O Chemical class O.[K].[N+](=O)([O-])C1=C(C(=O)O)NC(NC1=O)=O CXHLVSRLJAYJLY-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- IFOZXUMSHBVSMA-UHFFFAOYSA-N 5-nitro-2,4-dioxo-1h-pyrimidine-6-carboxylic acid;potassium Chemical compound [K].OC(=O)C=1NC(=O)NC(=O)C=1[N+]([O-])=O IFOZXUMSHBVSMA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 16
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- 230000003647 oxidation Effects 0.000 abstract description 12
- 235000015511 Liquidambar orientalis Nutrition 0.000 abstract description 10
- 239000004870 Styrax Substances 0.000 abstract description 10
- 235000000126 Styrax benzoin Nutrition 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- WJFDCFHWFHCLIW-UHFFFAOYSA-N 2-(bromomethyl)-6-methylpyridine Chemical compound CC1=CC=CC(CBr)=N1 WJFDCFHWFHCLIW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 244000028419 Styrax benzoin Species 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 241000736148 Styrax Species 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- OPGJGRWULGFTOS-UHFFFAOYSA-N 5-nitro-2,4-dioxo-1h-pyrimidine-6-carboxylic acid Chemical compound OC(=O)C=1NC(=O)NC(=O)C=1[N+]([O-])=O OPGJGRWULGFTOS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- -1 Transition-metal cation Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical compound [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- FJPYVLNWWICYDW-UHFFFAOYSA-M sodium;5,5-diphenylimidazolidin-1-ide-2,4-dione Chemical compound [Na+].O=C1[N-]C(=O)NC1(C=1C=CC=CC=1)C1=CC=CC=C1 FJPYVLNWWICYDW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
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- 238000004809 thin layer chromatography Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明公开了一种双核镍配合物及其制备方法,该镍配合物是一种具有准确空间结构,其结构单元为[Ni2(C5HN3O6)2(bpy)(H2O)6]·4H2O(bpy=4,4’‑二联吡啶),化学式为Ni2C20H30N8O22,晶系为三斜晶系,空间群为P‑1,晶胞参数为 α=109.695°,β=92.130°,γ=96.161°,镍离子为六配位的八面体几何构型。所述双核镍配合物的制备方法为:将5‑硝基乳清酸钾单水合物、4,4’‑二联吡啶配体与具有电化学活性的镍离子通过分层扩散法进行自组装反应,制得一种双核镍配合物。该制备方法操作简单,成本低廉,适合规模化生产。本发明所得的镍配合物作为催化氧化安息香制备苯偶酰的催化剂材料具有潜在的应用前景。
Description
技术领域
本发明属于材料化学领域,具体涉及一种双核镍配合物及其制备方法。
背景技术
过渡金属阳离子如Co2+、Ni2+、Cu2+等具有未充满的d轨道,容易和有机配体形成不同结构的配合物,这类配合物往往具有丰富的电化学性能,其作为催化剂能够催化氧化许多化学反应。例如,过渡金属配合物能够在温和的条件下高效催化氧化安息香合成苯偶酰,且能够回收套用。
苯偶酰,是有机合成重要原料,是合成药物苯妥英钠的中间体,亦可用于杀虫剂及紫外线固化树脂的光敏剂,在医药、香料、日用化学品生产中有着广泛的应用。合成苯偶酰的方法有很多,其中,最为常用的是由安息香催化氧化合成苯偶酰。以安息香类物质为原料合成苯偶酰,是目前工业生产上最为常用的方法。随着合成方法和技术的不断推新,一些新的氧化剂、催化氧化体系的研制极大地丰富和优化了苯偶酰类物质的合成路线。
用Fe2O3/A12O3催化氧化安息香来制备苯偶酰(蔡哲斌等人,有机化学,2002,22(6),446~449),发现该催化剂催化活性较高,以吡啶为溶剂,用483K下活化的含铁14.8%的氧化铁/三氧化二铝作催化剂,当其用量为苯偶酰用量20%,353K反应1h,苯偶酰平均产率80%以上。该研究结果表明,在催化剂存在条件下,空气为氧化剂氧化安息香的方法是可行的。然而,反应操作繁琐、溶剂污染严重等不足局限这种催化氧化方法的发展。积极探索简便高效的氧化手段,寻找新型替代催化剂就成了氧化反应的研究热点。
过渡金属配合物是一类典型的可逆氧载体,因其制备方法相对简单、结构易修饰、选择性好,越来越受研究学者们的关注。近年来,关于希夫碱配合物的报道日益增多,该类催化剂活性高,反应条件温和,可重复利用(单高峰等人,中南大学学报,2011,42(10),2959~2965;袁淑军等人,化学世界,2004,(5),233~235;丁成等人,浙江工业大学学报,2009,37(5),542~544)。希夫碱配合物作为催化剂在安息香的催化氧化实验中,催化剂可以回收套用是合成苯偶酰研究过程中的一大进步。在上述论述中,发现金属配合物作为催化剂进行回收套用的最佳使用次数为两次,在第三次使用时,收率有所降低。从目前研究水平来看,制备苯偶酰所用的方法中存在氧化剂用量大、分离提纯困难、污染严重等问题。近年来,对安息香氧化反应的研究始终围绕绿色化学的概念,积极探索简便高效的氧化手段,寻找新型替代催化剂。
本发明公开一种双核镍配合物,该配合物热稳定性好、制备操作方法简单、原料廉价易得。该配合物具有丰富的电化学活性,作为催化氧化安息香制备苯偶酰的催化剂材料具有潜在的应用前景。
发明内容
本发明所要解决的技术问题是针对现有技术,提供一种反应条件温和,制备过程简单,成本低廉,具有双核结构的镍配合物及其制备方法。
本发明为解决上述技术问题所采取的技术方案为:一种双核镍配位化合物(简称配合物),该配合物具有一定空间结构,其化学式为Ni2C20H30N8O22,其结构单元为[Ni2(C5HN3O6)2(bpy)(H2O)6]·4H2O(bpy=4,4’-二联吡啶),晶系为三斜晶系,空间群为P-1,晶胞参数为α=109.695°,β=92.130°,γ=96.161°,镍离子为六配位的八面体几何构型。
一种上述双核镍配合物的制备方法,包括以下步骤:
(1)称取一定量的水合醋酸镍,置于烧杯中,加适量的蒸馏水和乙醇,加热,搅拌,得溶液A;
(2)称取一定量的水合4,4’-二联吡啶,加适量的乙醇,加热,搅拌,得溶液B;称取一定量的5-硝基乳清酸钾单水合物,置于烧杯中,加适量的蒸馏水,搅拌,得溶液C;将溶液B和溶液C混合,得B+C混合溶液;
(3)将溶液A放入25mL的试管的底部,然后在溶液A的上部放置5mL的乙醇,在乙醇的上部放置B+C混合溶液,室温静置3~5天,得绿色块状晶体;
(4)将绿色块状晶体取出,自然风干,即得所述的镍配合物;
优选的,所述参加反应的物质的量比为:镍离子:4,4’-二联吡啶:5-硝基乳清酸钾=1∶1∶1;镍离子的浓度为0.0125~0.025 mmol/mL,5-硝基乳清酸钾的浓度为0.025~0.05mmol/mL,4,4’-二联吡啶的浓度为0.025~0.05 mmol/mL;
优选的,所述参加反应的物质均为化学纯,所述水合醋酸镍为四水合醋酸镍,水合4,4’-二联吡啶为二水合4,4’-二联吡啶。
与现有技术相比,本发明的特点在于:
将具有刚性平面共轭的4,4’-二联吡啶配体、硝基乳清酸与具有电化学活性的镍离子通过分层扩散法进行自组装反应,在反应中5-硝基乳清酸使用其氮和羧基氧与镍离子鳌合配位,4,4’-二联吡啶作为桥联配体连接两个镍离子,形成一种双核结构的镍配合物。在该配合物中,正二价镍离子Ni2+具有d8价电子结构,含有两个未充满的d轨道,能够产生d-d跃迁,因而具有电化学活性,该配合物作为催化氧化安息香制备苯偶酰的催化剂材料具有潜在的应用前景。
附图说明
图1为本发明的镍配合物的结构单元图(为图示清晰,碳原子和对称操作出来的原子没有标记)。
具体实施方式
以下结合附图实施例对本发明作进一步详细描述。
实施例1:
称取Ni(Ac)2·4H2O(0.1mmol,0.0249g),加入水4mL,加乙醇4mL,加热,搅拌,得溶液A;称取二水合4,4’-二联吡啶(0.1mmol,0.0192g),加乙醇4mL,加热,搅拌,得溶液B;称取5-硝基乳清酸钾单水合物(0.1mmol,0.0257g),加入蒸馏水4mL,加热,搅拌,得溶液C;将上述溶液B和溶液C混合,得B+C混合溶液;将溶液A放入25mL的试管的底部,然后在溶液A的上部放置5mL的乙醇,在乙醇的上部放置B+C混合溶液,室温静置5天,得绿色块状晶体;将绿色块状晶体取出,自然风干,即得所述的镍配合物。
实施例2:
称取Ni(Ac)2·4H2O(0.1mmol,0.0249g),加入水2mL,加乙醇2mL,加热,搅拌,得溶液A;称取二水合4,4’-二联吡啶(0.1mmol,0.0192g),加乙醇2mL,加热,搅拌,得溶液B;称取5-硝基乳清酸钾单水合物(0.1mmol,0.0257g),加入蒸馏水2mL,加热,搅拌,得溶液C;将上述溶液B和溶液C混合,得B+C混合溶液;将溶液A放入25mL的试管的底部,然后在溶液A的上部放置5mL的乙醇,在乙醇的上部放置B+C混合溶液,室温静置3天,得绿色块状晶体;将绿色块状晶体取出,自然风干,即得所述的镍配合物。
实施例3:
称取Ni(Ac)2·4H2O(0.1mmol,0.0249g),加入水2mL,加乙醇4mL,加热,搅拌,得溶液A;称取二水合4,4’-二联吡啶(0.1mmol,0.0192g),加乙醇4mL,加热,搅拌,得溶液B;称取5-硝基乳清酸钾单水合物(0.1mmol,0.0257g),加入蒸馏水4mL,加热,搅拌,得溶液C;将上述溶液B和溶液C混合,得B+C混合溶液;将溶液A放入25mL的试管的底部,然后在溶液A的上部放置5mL的乙醇,在乙醇的上部放置B+C混合溶液,室温静置4天,得绿色块状晶体;将绿色块状晶体取出,自然风干,即得所述的镍配合物。
将实施例1-3制得的绿色块状晶体进行结构测试,结果表明所得绿色块状晶体为具有双核结构的镍配合物,其结构单元如图1所示(为了图示清晰,碳原子和对称操作出来的原子没有标记)。所制得的双核镍配合物其化学式为Ni2C20H30N8O22,其结构单元为[Ni2(C5HN3O6)2(bpy)(H2O)6]·4H2O(bpy=4,4’-二联吡啶),晶系为三斜晶系,空间群为P-1,晶胞参数为 α=109.695°,β=92.130°,γ=96.161°,镍离子为六配位的八面体几何构型。
将实施例1-3制得双核镍配合物作为催化氧化安息香制备苯偶酰的催化剂进行催化反应:
在装配有搅拌器、回流冷凝管和空气导管的三颈瓶中,加入3.18g(0.015mol)安息香和N,N-二甲基甲酰胺(DMF)25mL,溶解后加入0.3g制得双核镍配合物作为催化剂和0.6gKOH添加剂,80℃油浴加热,通入空气进行氧化,利用薄层色谱跟踪反应进程(每十分钟点样一次);反应结束后,冷却到室温,调节反应液pH为3~4,加入水50mL,即析出固体,抽滤,用蒸馏水洗涤三次,得苯偶酰粗产品;将粗品用甲醇进行重结晶,得黄色针状晶体苯偶酰,产率85%。
收集上述催化反应的滤液,用KOH溶液将滤液调至中性,用CH2Cl2分次萃取,用旋转蒸发仪回收CH2Cl2,残液为含有双核镍配合物催化剂的DMF溶液,补加少量DMF后,加入安息香和氢氧化钾进行下一批安息香催化氧化的反应。循环利用三次后催化反应制得苯偶酰的产率约为75%。
Claims (2)
1.一种双核镍配合物,其特征在于,该配合物具有一定空间结构,其结构单元为[Ni2(C5HN3O6)2(bpy)(H2O)6]·4H2O,其中bpy=4,4’-二联吡啶,化学式为Ni2C20H30N8O22,晶系为三斜晶系,空间群为P-1,晶胞参数为 α=109.695°,β=92.130°,γ=96.161°,镍离子为六配位的八面体几何构型。
2.一种如权利要求1所述的双核镍配合物的制备方法,其特征在于,包括以下步骤:
(1)称取一定量的水合醋酸镍,置于烧杯中,加适量的蒸馏水和乙醇,加热,搅拌,得溶液A;
(2)称取一定量的水合4,4’-二联吡啶,加适量的乙醇,加热,搅拌,得溶液B;称取一定量的5-硝基乳清酸钾单水合物,置于烧杯中,加适量的蒸馏水,搅拌,得溶液C;将溶液B和溶液C混合,得B+C混合溶液;
(3)将溶液A放入25mL的试管的底部,然后在溶液A的上部放置5mL的乙醇,在乙醇的上部放置B+C混合溶液,室温静置3~5天,得绿色块状晶体;
(4)将绿色块状晶体取出,自然风干,即得所述的镍配合物;
所述参加反应的物质的量比为:镍离子:4,4’-二联吡啶:5-硝基乳清酸钾=1∶1∶1;镍离子的浓度为0.0125~0.025mmol/mL,5-硝基乳清酸钾的浓度为0.025~0.05mmol/mL,4,4’-二联吡啶的浓度为0.025~0.05mmol/mL;
优选的,所述参加反应的物质均为化学纯,所述水合醋酸镍为四水合醋酸镍,水合4,4’-二联吡啶为二水合4,4’-二联吡啶。
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