CN110964064A - 一类含吡啶甲基pnp配体的镍铁氢化酶模型物及其合成方法 - Google Patents
一类含吡啶甲基pnp配体的镍铁氢化酶模型物及其合成方法 Download PDFInfo
- Publication number
- CN110964064A CN110964064A CN201911333113.2A CN201911333113A CN110964064A CN 110964064 A CN110964064 A CN 110964064A CN 201911333113 A CN201911333113 A CN 201911333113A CN 110964064 A CN110964064 A CN 110964064A
- Authority
- CN
- China
- Prior art keywords
- solvent
- acetone
- picolyl
- ligand
- pnp
- 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.)
- Pending
Links
- 239000003446 ligand Substances 0.000 title claims abstract description 35
- 150000001875 compounds Chemical class 0.000 title claims abstract description 14
- 108010092755 nickel-iron hydrogenase Proteins 0.000 title claims description 12
- 238000010189 synthetic method Methods 0.000 title abstract description 4
- 229910000863 Ferronickel Inorganic materials 0.000 claims abstract description 30
- 108010020056 Hydrogenase Proteins 0.000 claims abstract description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- -1 tetrafluoroborate Chemical group 0.000 claims abstract 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 72
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 48
- 239000002904 solvent Substances 0.000 claims description 37
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 16
- NCKJIJSEWKIXAT-DQRAZIAOSA-N [(z)-2-diphenylphosphanylethenyl]-diphenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)/C=C\P(C=1C=CC=CC=1)C1=CC=CC=C1 NCKJIJSEWKIXAT-DQRAZIAOSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000004809 thin layer chromatography Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000006418 Brown reaction Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910020808 NaBF Inorganic materials 0.000 claims description 6
- PGFPZGKEDZGJQZ-UHFFFAOYSA-N n,n-dimethylmethanamine oxide;dihydrate Chemical compound O.O.C[N+](C)(C)[O-] PGFPZGKEDZGJQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 claims description 4
- 229910004039 HBF4 Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LNVWRBNPXCUYJI-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazol-4-amine Chemical compound CC1=NNC(C)=C1N LNVWRBNPXCUYJI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021135 KPF6 Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000006392 deoxygenation reaction Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 13
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000004679 31P NMR spectroscopy Methods 0.000 description 6
- 229910018104 Ni-P Inorganic materials 0.000 description 6
- 229910018536 Ni—P Inorganic materials 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000005344 pyridylmethyl group Chemical group [H]C1=C([H])C([H])=C([H])C(=N1)C([H])([H])* 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical group 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 238000001308 synthesis method Methods 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
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyridine Compounds (AREA)
- Enzymes And Modification Thereof (AREA)
Abstract
Description
技术领域
本发明属于金属有机和能源科学技术领域,特别是一类含吡啶甲基PNP配体的镍铁氢化酶模型物及其合成方法。
背景技术
氢能源是一种清洁、零碳、高效的可再生能源,它具有重量轻、导热性好和燃烧性好等特点。面对日益严重的能源匮乏和环境污染问题,世界上许多国家都将发展氢能源作为本国社会和经济发展的一项重大战略任务。鉴于镍铁氢化酶可在温和的条件下高效催化质子还原产氢,因此人们期望通过镍铁氢化酶仿生化学的研究,合成一种价廉高效的产氢催化剂,以解决人类面临的能源短缺和环境污染问题。(Cook,T.R.;Dogutan,D.K.;Reece,S.Y.;Surendranath,Y.;Teets,T.S.;Nocera,D.G.Chem.Rev.2010,110,6474-6502.Lubitz,W.;Ogata,H.;Rüdiger,O.;Reijerse,E.;Chem.Rev.2014,114,4081-4148.)
自从镍铁氢化酶的活性中心结构确定以来,科学家们通过对镍铁氢化酶仿生化学的研究,合成了许多在金属镍原子和铁原子周围含多种配体的镍铁氢化酶模型物,但是至今尚无含吡啶甲基PNP配体的镍铁氢化酶模型物的报道。(Royer,A.M.;Salomone-Stagni,M.;Rauchfuss,T.B.;Meyer-Klaucke,W.J.Am.Chem.Soc.2010,132,16997-17003.Ogo,S.;Ichikawa,K.;Kishima,T.;Matsumoto,T.;Nakai,H.;Kusaka,K.;Ohhara,T.Science 2013,339,682-684.Manor,B.C.;Rauchfuss,T.B.J.Am.Chem.Soc.2013,135,11895-11900.Schilter,D.;Camara,J.M.;Huynh,M.T.;Hammes-Schiffer,S.;Rauchfuss,T.B.Chem.Rev.2016,116,8693.Song,L.-C.;Yang,X.-Y.;Cao,M.;Gao,X.-Y.;Liu,B.-B.;Zhu,L.;Jiang,F.Chem.Commun.2017,53,3818-3821.Song,L.-C.;Gao,X.-Y.;Liu,W.-B.;Zhang,H.-T.;Cao,M.Organometallics,2018,37,1050-1061.)
发明内容
本发明的目的是解决现有技术中尚未合成含吡啶甲基PNP配体的镍铁氢化酶模型物的方法,提供一类含这种配体的镍铁氢化酶模型物及其合成方法。该方法所需原料价廉易得、反应条件温和、操作简便、产率高,可制备多种含这种配体的新型镍铁氢化酶模型物。这类模型物不仅结构新颖,而且具有潜在优良催化产氢功能。
本发明的技术方案:
一类含吡啶甲基PNP配体的镍铁氢化酶模型物,其化学结构式如下所示:
在以上结构式中:R为CO、OH、H、CH3CN、CH3COS或PhS,阴离子X为四氟硼酸根或六氟磷酸根,n值为1或2。
制备这类含吡啶甲基PNP配体的镍铁氢化酶模型物的方法如下:
1)在氩气保护的条件下,向装有化合物[(dppv)Fe(CO)2(pdt)][dppv=顺-1,2-双(二苯基磷基)乙烯,pdt=1,3-丙二硫配体],化合物(PNP)NiCl2[PNP=C5H4NCH2N(PPh2)2]和化合物NaBF4的带有搅拌磁子的反应瓶中加入无水除氧丙酮溶剂,室温下搅拌反应,得到混合液;
2)将上述反应液减压抽干溶剂,用二氯甲烷和丙酮作为展开剂进行薄层色谱分离,收集红色主带,减压除去溶剂得红色固体即R为CO的镍铁氢化酶模型物;
3)如果向步骤1)的混合液中加入二水合氧化三甲胺,室温下反应0.5h,则得到棕色反应液。将该反应液减压抽干溶剂,用二氯甲烷和丙酮作为展开剂进行薄层色谱分离,收集棕色主带,得棕色固体即为含μ-OH配体的镍铁氢化酶模型物;
4)在步骤3)所述棕色反应液中加入HBF4·Et2O和H2,室温下反应18h,得到的反应液;减压抽干溶剂,用二氯甲烷和丙酮作为展开剂进行薄层色谱分离,收集棕色主带,得棕色固体即为含μ-H配体的镍铁氢化酶模型物;
5)如果向步骤1)的混合液中加入氧化三甲胺和乙腈溶剂,室温下反应0.5h得到的棕色反应液浓缩至3mL,然后多次用乙醚重结晶,减压除去溶剂,得棕色固体即为含乙腈配位的镍铁氢化酶模型物;
6)如果向在步骤5)所述反应液中加入KPF6和CH3COSK或PhSNa,室温下反应2h,则分别得到相应的棕色反应液;进一步将这些反应液减压抽干溶剂,用二氯甲烷和丙酮作为展开剂进行薄层色谱分离,收集棕色主带,得棕色固体物质分别为含硫配体CH3COS或PhS的镍铁氢化酶模型物;
所述步骤1)中[(dppv)Fe(CO)2(pdt)]、(PNP)NiCl2、NaBF4和有机溶剂的用量比为0.5mmol:0.5mmol:5mmol:30mL。
所述步骤2)中展开剂中二氯甲烷和丙酮的体积比为20:1。
所述步骤3)中NaBF4和二水合氧化三甲胺的用量比为5mmol:0.5mmol,展开剂中二氯甲烷和丙酮的体积比为5:1。
所述步骤4)中二水合氧化三甲胺、KPF6和HBF4·Et2O的用量比为0.5mmol:1.0mmol:0.1mL,H2的压力为4Mpa,展开剂中二氯甲烷和丙酮的体积比为10:1。
所述步骤5)中NaBF4和氧化三甲胺、乙腈的用量比为5mmol:0.5mmol:10mL。
所述步骤6)中NaBF4、KPF6和CH3COSK或PhSNa的用量比为5mmol:1.0mmol:0.5mmol,展开剂中二氯甲烷和丙酮的体积比为15:1。
本发明的有益效果是:该方法制备含吡啶甲基PNP配体的镍铁氢化酶模型物,所需原料价廉易得、反应条件温和、操作简便而且产率高。该方法适用于合成含多种不同桥连配体的镍铁氢化酶模型物,具有潜在的优良催化产氢功能。
具体实施方式
为更好地理解本发明,下面将通过具体的实施例进一步说明本发明的方案,但本发明的保护范围应包括权利要求的全部内容,不限于此。
实施例1:
含吡啶甲基PNP配体的镍铁氢化酶模型物1的制备方法,所述模型物1的化学式为[(dppv)Fe(CO)2(pdt)Ni(PNP)(BF4)2],制备过程如下所示:
具体制备步骤如下:
1)在氩气保护的条件下,称取307mg(0.5mmol)化合物[(dppv)Fe(CO)2(pdt)],302mg(0.5mmol)化合物(PNP)NiCl2和550mg(5mmol)化合物NaBF4于100mL带有搅拌磁子的Schlenk瓶中,并加入30mL无水除氧丙酮溶剂,室温下反应5h;
2)将上述反应液减压抽干溶剂,用适量的二氯甲烷提取残余物,接着用二氯甲烷/丙酮=20:1(v/v)作为展开剂进行薄层色谱分离,收集红色主带,最后减压除去溶剂得433mg红色固体1,产率65%。
产物表征数据如下:Anal.Calcd for C61H54B2F8FeN2NiOP4S2:C,55.37;H,4.11;N,2.12.Found:C,55.54;H,4.51;N,2.21.IR(KBr disk):νC≡O:1988(vs),2054(m).1H NMR(400MHz,acetone-d6):2.29-2.65(m,6H,SCH2CH2CH2S);3.87(t,J=12Hz,2H,NCH2);6.12(d,J=4Hz,1H,3-H of C5H3N);6.80(t,J=4Hz,1H,5-H of C5H3N);7.14-7.73(m,42H,8C6H5and 4,6-H of C5H4N);8.19-8.34(m,2H,PCH=CHP).ppm.13C NMR(100MHz,CDCl3):30.1,31.0,36.8(3s,SCH2CH2CH2S);67.1(s,NCH2);123.6—152.5(m,CH=CH,C6H5,C5H4N);206.1,207.2(2s,C≡O)ppm.31P NMR(161.9MHz,acetone-d6):65.58(s,Fe-P);53.84(s,Ni-P)ppm。
实施例2:
含吡啶甲基PNP配体的镍铁氢化酶模型物2的制备方法,所述模型物2的化学式为[(dppv)Fe(CO)(μ-OH)(pdt)Ni(PNP)(BF4)],制备过程如下所示:
具体制备步骤如下:
1)在氩气保护的条件下,称取666mg(0.5mmol)模型物1和55.5mg(0.5mmol)的Me3NO·2H2O(二水合氧化三甲胺)于100mL带有搅拌磁子的Schlenk瓶中,并加入30mL无水除氧丙酮溶剂,室温下反应0.5h,得混合液;
2)将上述反应液减压抽干溶剂,用适量的二氯甲烷提取残余物,接着用二氯甲烷/丙酮=5:1(v/v)作为展开剂进行薄层色谱分离,收集棕色主带,最后减压除去溶剂得465mg棕色固体2,产率76%。
产物表征数据如下:Anal.Calcd for C60H55BF4FeN2NiO2P4S2:C,58.81;H,4.52;N,2.29.Found:C,58.82;H,4.71;N,1.94.IR(KBr disk):νC≡O:1928(m);νOH:3409(w).1H NMR(400MHz,acetone-d6):-3.91(s,1H,OH);1.63-1.67,2.14-2.84(2m,6H,SCH2CH2CH2S),3.85(t,J=12Hz,2H,NCH2);6.43(d,J=8Hz,1H,3-H of C5H3N);7.05(d,J=8Hz,1H,5-H ofC5H3N);7.28-7.90(m,42H,4C6H5 and 4,6-H of C5H4N);8.18-8.32(m,2H,PCH=CHP)ppm.13CNMR(100MHz,acetone-d6):25.7,36.8,46.2(3s,SCH2CH2CH2S);54.0(s,NCH2);123.9—155.4(m,CH=CH,C6H5 and C5H4N);216.4(s,C≡O)ppm.31P NMR(161.9MHz,acetone-d6):79.81(s,Fe-P);49.65(s,Ni-P)ppm。
实施例3:
含吡啶甲基PNP配体的镍铁氢化酶模型物3的制备方法,所述模型物3的化学式为[(dppv)Fe(CO)(μ-H)(pdt)Ni(PNP)(PF6)],制备过程如下所示:
具体制备步骤如下:
1)在氩气保护的条件下,称取667.5mg(0.5mmol)模型物2、184mg(1.0mmol)的KPF6和0.1mL HBF4·Et2O于30mL带有搅拌磁子的高压釜芯中,并向高压釜中充入4Mpa氢气,室温下反应18h,得反应液;
2)将上述反应液减压抽干溶剂,用适量的二氯甲烷提取残余物,接着用二氯甲烷/丙酮=10:1(v/v)作为展开剂进行薄层色谱分离,收集棕色主带,最后减压除去溶剂得184mg棕色固体3,产率30%。
产物表征数据如下:Anal.Calcd for C60H55F4FeN2NiOP5S2:C,58.61;H,4.51;N,2.28.Found:C,58.56;H,4.35;N,2.31.IR(KBr disk):νC≡O:1942(s).1H NMR(400MHz,acetone-d6):-7.68(t,J=32Hz,1H,Fe-H);2.23-2.81(m,6H,SCH2CH2CH2S);4.05(t,J=12Hz,2H,NCH2);6.25(d,J=8Hz,1H,3-H of C5H3N);7.06-7.80(m,45H,4,5,6-H of C5H3N,8C6H5 and 2H of PCH=CHP)ppm.13C NMR(100MHz,acetone-d6):25.7,36.8,46.1(3s,SCH2CH2CH2S);54.0(s,NCH2);123.9—155.4(m,CH=CH,C6H5 and C5H4N);216.4(s,C≡O)ppm.31P NMR(161.9MHz,acetone-d6):84.16(s,Fe-P);63.36(s,Ni-P);-144.24(qui.,PF6)ppm。
实施例4:
含吡啶甲基PNP配体的镍铁氢化酶模型物4的制备方法,所述模型物4的化学式为[(dppv)Fe(CO)(CH3CN)(pdt)Ni(PNP)(BF4)2],制备过程如下所示:
具体制备步骤与实施例2基本相同,不同之处在于:
步骤1)中加入的Me3NO·2H2O改为37.5mg(0.5mmol)的Me3NO(氧化三甲胺)和10mL无水除氧乙腈溶剂;
步骤2)中改为将上述反应液浓缩至3mL,然后多次用乙醚重结晶,减压除去溶剂得641mg棕色固体4,产率96%。
产物表征数据如下:Anal.Calcd for C62H57B2F8FeN3NiOP4S2:C,55.73;H,4.30;N,3.14.Found:C,55.88;H,4.60;N,3.55.IR(KBr disk):νC≡O:1968(s).1H NMR(400MHz,CD3CN):1.96(s,3H,CH3CN);2.65-3.28(m,6H,SCH2CH2CH2S);4.18(t,J=12Hz,2H,NCH2);6.37(d,J=4Hz,1H,3-H of C5H3N);6.98(t,J=4Hz,1H,5-H of C5H3N);7.35-7.89(m,42H,8C6H5,4,6-H of C5H4N);8.24-8.38(m,2H,PCH=CHP)ppm.13C NMR(100MHz,CD3CN):15.2,31.2,37.4(3s,SCH2CH2CH2S);53.9(s,CH3CN);65.8(s,NCH2);124.2—153.4(m,CN,CH=CH,C6H5,C5H4N);215.1(s,C≡O)ppm.31P NMR(161.9MHz,CD3CN):73.62(s,Fe-P);53.81(s,Ni-P)ppm。
实施例5:
含吡啶甲基PNP配体的镍铁氢化酶模型物5的制备方法,所述模型物5的化学式为[(dppv)Fe(CO)(μ-SCOCH3)(pdt)Ni(PNP)(PF6)],制备过程如下所示:
具体制备步骤如下:
1)在氩气保护的条件下,称取667.5mg(0.5mmol)模型物4,、184mg(1.0mmol)的KPF6和57mg(0.5mmol)的CH3COSK,室温下反应2h,得反应液;
2)将上述反应液减压抽干溶剂,用适量的二氯甲烷提取残余物,接着用二氯甲烷/丙酮=15:1(v/v)作为展开剂进行薄层色谱分离,收集棕色主带,最后减压除去溶剂得435.5mg棕色固体5,产率65%。
产物表征数据如下:Anal.Calcd for C62H57F6FeN2NiO2P5S3:C,55.50;H,4.28;N,2.09.Found:C,55.45;H,4.39;N,2.06.IR(KBr disk):νC≡O:1942(s);νC=O:1587(m).1H NMR(400MHz,acetone-d6):2.14-2.60(m,6H,SCH2CH2CH2S);2.83(s,3H,CH3C=O);4.26(t,J=12Hz,2H,NCH2);6.52(d,J=8Hz,1H,3-H of C5H3N);7.07-8.03(m,43H,8C6H5 and 4,5,6-Hof C5H4N);8.31-8.45(m,2H,PCH=CHP)ppm.13C NMR(100MHz,acetone-d6):30.7,34.9,36.1(3s,SCH2CH2CH2S);54.22(s,NCH2);124.3—154.9(m,CH=CH,C6H5 and C5H4N);200.3(s,CH3C=O);215.6(s,C≡O)ppm.31P NMR(161.9MHz,acetone-d6):72.29(s,Fe-P);56.33(s,Ni-P);-144.22(qui.,PF6)ppm。
实施例6:
含吡啶甲基PNP配体的镍铁氢化酶模型物6的制备方法,所述模型物6的化学式为[(dppv)Fe(CO)(μ-SPh)(pdt)Ni(PNP)(PF6)],制备过程如下所示:
具体制备步骤与实施例5基本相同,不同之处在于:
步骤1)中加入的CH3COSK改为66mg(0.5mmol)化合物C6H5SNa;
步骤2)中得到364mg棕色固体6,产率53%。
产物表征数据如下:Anal.Calcd for C66H59F6FeN2NiOP5S3:C,57.62;H,4.32;N,2.04.Found:C,57.37;H,4.37;N,2.06.IR(KBr disk):νC≡O:1955(s).1H NMR(400MHz,acetone-d6):1.20-1.40,2.23-2.8(2m,6H,SCH2CH2CH2S);2.82-2.85(m,2H,NCH2);6.42(d,J=8Hz,1H,3-H of C5H3N);6.73(t,J=8Hz,1H,5-H of C5H3N);6.97-8.48(m,49H,9C6H5 and4,6-H of C5H4N,PCH=CHP)ppm.13C NMR(100 MHz,CDCl3):26.1,28.7,33.1(3s,SCH2CH2CH2S);54.5(s,NCH2);122.2—148.3(m,CH=CH,C6H5 and C5H4N);212.4(s,C≡O)ppm.31P NMR(161.9 MHz,acetone-d6):79.47,74.85(d,Fe-P);49.08(s,Ni-P);-144.35(qui.,PF6)ppm。
Claims (8)
2.一种如权利要求1所述含吡啶甲基PNP配体的镍铁氢化酶模型物的制备方法,其特征在于步骤如下:
1)在氩气保护的条件下,向装有化合物[(dppv)Fe(CO)2(pdt)]、化合物(PNP)NiCl2和化合物NaBF4的带有搅拌磁子的反应瓶中加入无水除氧丙酮溶剂,室温下搅拌反应,得到混合液;
2)将上述反应液减压抽干溶剂,用二氯甲烷和丙酮作为展开剂进行薄层色谱分离,收集红色主带,减压除去溶剂得红色固体即R为CO的镍铁氢化酶模型物;
3)如果向步骤1)的混合液中加入化合物二水合氧化三甲胺,室温下反应0.5h,则得到棕色反应液。将该反应液减压抽干溶剂,用二氯甲烷和丙酮作为展开剂进行薄层色谱分离,收集棕色主带,得棕色固体即为含μ-OH配体的镍铁氢化酶模型物;
4)在步骤3)所述棕色反应液中加入HBF4·Et2O和H2,室温下反应18h,得到的反应液;减压抽干溶剂,用二氯甲烷和丙酮作为展开剂进行薄层色谱分离,收集棕色主带,得棕色固体即为含μ-H配体的镍铁氢化酶模型物;
5)如果向步骤1)的混合液中加入化合物氧化三甲胺和乙腈溶剂,室温下反应0.5h得到的棕色反应液浓缩至3mL,然后多次用乙醚重结晶,减压除去溶剂,得棕色固体即为含乙腈配位的镍铁氢化酶模型物;
6)如果向在步骤5)所述反应液中加入KPF6和CH3COSK或PhSNa,室温下反应2h,则分别得到相应的棕色反应液;进一步将这些反应液减压抽干溶剂,用二氯甲烷和丙酮作为展开剂进行薄层色谱分离,收集棕色主带,得棕色固体物质分别为含硫配体CH3COS或PhS的镍铁氢化酶模型物。
3.根据权利要求2所述含吡啶甲基PNP配体的镍铁氢化酶模型物的制备方法,其特征在于:步骤1)中[(dppv)Fe(CO)2(pdt)]、(PNP)NiCl2、NaBF4和有机溶剂的用量比为0.5mmol:0.5mmol:5mmol:30mL。
4.根据权利要求2所述含吡啶甲基PNP配体的镍铁氢化酶模型物的制备方法,其特征在于:步骤2)中展开剂中二氯甲烷和丙酮的体积比为20:1。
5.根据权利要求2所述含吡啶甲基PNP配体的镍铁氢化酶模型物的制备方法,其特征在于:步骤3)中NaBF4和二水合氧化三甲胺的用量比为5mmol:0.5mmol,展开剂中二氯甲烷和丙酮的体积比为5:1。
6.根据权利要求2所述含吡啶甲基PNP配体的镍铁氢化酶模型物的制备方法,其特征在于:步骤4)中二水合氧化三甲胺、KPF6和HBF4·Et2O的用量比为0.5mmol:1.0mmol:0.1mL,H2的压力为4Mpa,展开剂中二氯甲烷和丙酮的体积比为10:1。
7.根据权利要求2所述含吡啶甲基PNP配体的镍铁氢化酶模型物的制备方法,其特征在于:步骤5)中NaBF4和氧化三甲胺、乙腈的用量比为5mmol:0.5mmol:10mL。
8.根据权利要求2所述含吡啶甲基PNP配体的镍铁氢化酶模型物的制备方法,其特征在于:步骤6)中NaBF4和KPF6、CH3COSK或PhSNa的用量比为5mmol:1.0mmol:0.5mmol,展开剂中二氯甲烷和丙酮的体积比为15:1。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911333113.2A CN110964064A (zh) | 2019-12-23 | 2019-12-23 | 一类含吡啶甲基pnp配体的镍铁氢化酶模型物及其合成方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911333113.2A CN110964064A (zh) | 2019-12-23 | 2019-12-23 | 一类含吡啶甲基pnp配体的镍铁氢化酶模型物及其合成方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110964064A true CN110964064A (zh) | 2020-04-07 |
Family
ID=70035851
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911333113.2A Pending CN110964064A (zh) | 2019-12-23 | 2019-12-23 | 一类含吡啶甲基pnp配体的镍铁氢化酶模型物及其合成方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110964064A (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104530141A (zh) * | 2015-01-09 | 2015-04-22 | 南开大学 | 一种含丙二硫桥配体的镍铁氢化酶模型物及其制备方法 |
-
2019
- 2019-12-23 CN CN201911333113.2A patent/CN110964064A/zh active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104530141A (zh) * | 2015-01-09 | 2015-04-22 | 南开大学 | 一种含丙二硫桥配体的镍铁氢化酶模型物及其制备方法 |
Non-Patent Citations (2)
Title |
---|
LI-CHENG SONG等: "Synthesis, Characterization, and Reactions of Functionalized Nickel−Iron Dithiolates Related to the Active Site of [NiFe]-Hydrogenases", 《ORGANOMETALLICS》 * |
李嘉鹏: "[NiFe]氢化酶活性中心模型物的合成、结构表征及性质研究", 《南开大学博士学位论文》 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Wu et al. | Copper (i) iodide cluster-based lanthanide organic frameworks: synthesis and application as efficient catalysts for carboxylative cyclization of propargyl alcohols with CO 2 under mild conditions | |
JP6516856B2 (ja) | ホルムアミド系化合物を製造する方法 | |
Tian et al. | A highly stable polyoxovanadate-based Cu (I)–MOF for the carboxylative cyclization of CO 2 with propargylic alcohols at room temperature | |
Cui et al. | Solvent-free heterogeneous catalysis for cyanosilylation in a dynamic cobalt-MOF | |
CN105753700B (zh) | 一种乙炔羰基化合成丙烯酸甲酯的方法 | |
Lavigne et al. | Aspects of the chemistry of substituted ruthenium clusters involving bis (diphenylphosphino)-or bis (diphenylarsino) methane as bridging ligands. Reactivity toward hydrogen and potential applications in catalysis. Crystal and molecular structure of (. mu.-H) 2Ru3 (CO) 6 (. mu.-P (C6H5) CH2P (C6H5) 2) 2 and (. mu.-H) 2Ru3 (CO) 6 (. mu.-As (C6H5) CH2As (C6H5) 2) 2 | |
Bansal et al. | Heterometallic coordination polymers: syntheses, structures and heterogeneous catalytic applications | |
Karmakar et al. | Synthesis and catalytic activities of a Zn (II) based metallomacrocycle and a metal–organic framework towards one-pot deacetalization-Knoevenagel tandem reactions under different strategies: A comparative study | |
CN109369689B (zh) | 一种铜金属有机框架(Cu-MOF)催化材料、制备方法及应用 | |
Guzmán et al. | Ir-catalyzed selective reduction of CO 2 to the methoxy or formate level with HSiMe (OSiMe 3) 2 | |
CN106854159A (zh) | 一种苯乙炔羰基化合成不饱和芳香酯的方法 | |
CN108722488B (zh) | 一种增强路易斯酸性的双金属中心金属-有机框架材料及其制备方法 | |
CN113004326B (zh) | 一种用于丁二烯氢甲酰化反应的膦配体及其制备方法 | |
Mochida et al. | Ferrocenylpyrazole—A versatile building block for hydrogen-bonded organometallic supramolecular assemblies | |
CN110964064A (zh) | 一类含吡啶甲基pnp配体的镍铁氢化酶模型物及其合成方法 | |
Darensbourg et al. | Preparation and structure of W (CO) 5OPPh2NPPh3, a novel complex containing a ligand derived from the bis (triphenylphosphine) nitrogen (1+) cation | |
CN115873263B (zh) | 一种金属有机框架材料及其制备方法和应用 | |
CN108623493B (zh) | 一种温和条件下以co2为碳源的n-甲酰化合成方法 | |
CN109111392B (zh) | 一种环丁烷衍生物的合成方法 | |
CN114653404A (zh) | 一种钌化合物催化剂及其在烯烃复分解中的用途 | |
CN114702517A (zh) | 一种壳聚糖席夫碱负载二价铜材料在制备β-硼基酯中的应用 | |
CN107987280B (zh) | 一种芳香磺酸镉配合物、制备方法及其应用 | |
CN109651446B (zh) | 一种单膦取代桥连氮杂丙烷桥铁铁氢化酶模型物及其合成方法和应用 | |
CN106349249A (zh) | 一种去甲斑蝥素衍生物的绿色合成方法 | |
CN108484686A (zh) | 一类含1,2-双(二苯基膦)苯和不同络阴离子的镍铁氢化酶模型物及制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200407 |