CN108516994A - 含双膦配体和桥连三硫配体双(硫乙基)硫醚[NiFe]氢化酶模型物及合成方法 - Google Patents
含双膦配体和桥连三硫配体双(硫乙基)硫醚[NiFe]氢化酶模型物及合成方法 Download PDFInfo
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- 229910001030 Iron–nickel alloy Inorganic materials 0.000 title claims abstract description 29
- KYLIZBIRMBGUOP-UHFFFAOYSA-N Anetholtrithion Chemical group C1=CC(OC)=CC=C1C1=CC(=S)SS1 KYLIZBIRMBGUOP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000010189 synthetic method Methods 0.000 title claims abstract description 8
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 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 abstract description 35
- 239000005864 Sulphur Substances 0.000 claims abstract description 24
- 150000003568 thioethers Chemical class 0.000 claims abstract description 24
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 28
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
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- FDSGHYHRLSWSLQ-UHFFFAOYSA-N dichloromethane;propan-2-one Chemical compound ClCCl.CC(C)=O FDSGHYHRLSWSLQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
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- 238000006392 deoxygenation reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ZBQUMMFUJLOTQC-UHFFFAOYSA-N dichloronickel;3-diphenylphosphaniumylpropyl(diphenyl)phosphanium Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1[PH+](C=1C=CC=CC=1)CCC[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 ZBQUMMFUJLOTQC-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- MPMYQQHEHYDOCL-UHFFFAOYSA-N [NaH] Chemical compound [NaH] MPMYQQHEHYDOCL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 2
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- 238000004679 31P NMR spectroscopy Methods 0.000 description 8
- 229910018104 Ni-P Inorganic materials 0.000 description 8
- 229910018536 Ni—P Inorganic materials 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000000547 structure data Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 0 CCC1(CC2)S[Fe](C)(*)(P/C=C/F)S2C1 Chemical compound CCC1(CC2)S[Fe](C)(*)(P/C=C/F)S2C1 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
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- 235000008434 ginseng Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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Abstract
一种含双膦配体和桥连三硫配体双(硫乙基)硫醚[NiFe]氢化酶模型物及合成方法，这种模型物使用[BF4‑]作为阴离子，而且模型物的铁中心只有一个羰基，使模型物具有反应的专一性。化学结构式如下所示：结构式中L1,L2为[(dppe)＝1,2‑双(二苯基膦)乙烷]，[(dppv)＝1,2‑双(二苯基膦)乙烯]，[(dppp)＝1,3‑双(二苯基膦)丙烷]，[(dppb)＝1,4‑双(二苯基膦)丁烷]。本发明的有益效果是:制备模型物的反应条件温和、工艺简便、原料廉价易得、收率较高，可制备多种含双膦配体和桥连三硫配体双(硫乙基)硫醚的[NiFe]氢化酶模型物。
Description
技术领域
本发明属于金属有机﹑能源科学和材料科学领域，特别是一种含双(硫乙基)硫醚的[NiFe]氢化酶模型物及其合成方法。
背景技术
众所周知，能源问题和环境问题已经成为制约经济发展和社会进步的重要因素，发展绿色的﹑环境友好型新能源迫在眉睫。氢气因具备可再生、燃烧值高及燃烧后只生成水等优点，成为公认的理想能源，但因传统制氢方法能耗大且污染严重，氢能源并不能广泛使用。科学家们发现自然界中存在可以高效催化水中质子还原为氢气的金属酶，并用X-射线晶体衍射法确定他们的分子结构，自从天然[NiFe]氢化酶的分子结构得到确认后，关于[NiFe]氢化酶活性中心的模拟合成已经有大量的报道，以期望研发出高效廉价催化剂，实现氢能源的大规模使用，参见：Volbeda,A.；Charon,M.-H.；Piras,C.；Hatchikian,E.C.；Frey,M.；Fontecilla-Campus,J.C.Nature.1995,373,580.Hu,Y.；Shaw,A.P.；Estes,D.P.；Norton,J.R.Chem.Rev.,2016,116,8427–8462.Ogata,H.；Nishikawa,K.；Lubitz,W.Nature.2015,520,571–574.Lubitz,W；Reijerse,E.；Gastel,M.V.Chem.Rev.2007,107,4331-4365.Vignais,P.M.；Billoud,B.Chem.Rev.2007,107,4206-4272.
到目前为止，使用桥连双硫配体的[NiFe]氢化酶模型物已经有了大量的报道。参见：Ulloa,O.A.；Huynh,M.T.；Richers,C.P.；Bertke,J.A.；Nilges,M.J.；Hammes-Schiffer,S.；Rauchfuss,T.B.J.Am.Chem.Soc.2016,138,9234-9245.Barton,B.E.；Whaley,C.M.；Rauchfuss,T.B.；Gray,D.L.J.Am.Chem.Soc.2009,131,6942–6943.Song,L.-C.；Han,X.-F.；Chen,W.；Li,J.-P.；Wang,X.-Y.DaltonTrans.,2017,46,10003-10013.但是，含双膦配体和桥连三硫配体双(硫乙基)硫醚的[NiFe]氢化酶模型物却从未见文献报道。
发明内容
本发明的目的是针对上述技术分析，提供一种含双(硫乙基)硫醚的[NiFe]氢化酶模型物及其合成方法。
为了合成具有优良催化产氢功能的新型[NiFe]氢化酶模型物，设计合成了首批含双膦配体和桥连三硫配体双(硫乙基)硫醚的[NiFe]氢化酶模型物，这种模型物使用[BF4 -]作为阴离子，而且模型物的铁中心只有一个羰基，使模型物具有反应的专一性。该制备方法操作简便，反应条件温和，原料廉价易得，产率较高，所合成的模型物具有优良的潜在催化产氢功能。
为了达到上述目的，本发明的技术方案：
一种含双膦配体和桥连三硫配体双(硫乙基)硫醚[NiFe]氢化酶模型物，这种模型物使用[BF4 -]作为阴离子，而且模型物的铁中心只有一个羰基，使模型物具有反应的专一性。该制备方法操作简便，反应条件温和，原料廉价易得，产率较高，所合成的模型物具有优良的潜在催化产氢功能。
化学结构式如下所示：
结构式中L1,L2为[(dppe)＝1,2-双(二苯基膦)乙烷]或[(dppv)＝1,2-双(二苯基膦)乙烯]或[(dppp)＝1,3-双(二苯基膦)丙烷]或[(dppb)＝1,4-双(二苯基膦)丁烷]。
一种所述含双膦配体和桥连三硫配体双(硫乙基)硫醚的[NiFe]氢化酶模型物合成方法，步骤如下：
1)在手套箱称取[FeCl2]于一个三口烧瓶中，氮气保护下，加入除氧的丙酮，通入CO，得淡黄色悬浮液，称取[dppe]或者[dppv]溶于除水除氧的四氢呋喃，室温下搅拌，溶液变为红色；
2)另称取氢化钠加入到一个反应瓶中，加入除水除氧的四氢呋喃，滴加双(巯乙基)硫醚，反应4h后，加入到上述溶液中，搅拌得反应液；
3)反应结束后，过滤，抽干溶剂得红色固体[(dppe)FeS3CO]或暗红色固体[(dppv)FeS3CO]；
4)在装有磁子的Schlenk反应瓶中，加入[(dppe)FeS3CO]或者[(dppv)FeS3CO]；氮气保护下；
5)向上述反应瓶中加入[NaBF4]，[(dppe)NiCl2]或者[(dppv)NiCl2]或者[(dppp)NiCl2]或者[(dppb)NiCl2]；
6)向上述反应瓶中加入丙酮，搅拌得到混合液，在室温下反应6h，得到反应液；
7)将上述反应液减压抽干，用体积比为12:1的二氯甲烷-丙酮混合液作为展开剂进行薄层色谱分离，收集主色带，减压抽干得到橙黄色固体即为含双(硫乙基)硫醚[NiFe]类氢化酶模型物1或5；
所述步骤2)中[FeCl2]、[dppe]、[NaH]和双(巯乙基)硫醚之间的摩尔量比为1:1:3:1。
所述步骤5)中[(dppe)FeS3CO]与[NaBF4]、[(dppe)NiCl2]之间的摩尔量比为1:10:1；[(dppe)FeS3CO]与[NaBF4]、[(dppv)NiCl2]之间的摩尔量比为1:10:1；[(dppe)FeS3CO]与[NaBF4]、[(dppp)NiCl2]之间的摩尔量比为1:10:1；[(dppe)FeS3CO]与[NaBF4]、[(dppb)NiCl2]之间的摩尔量比为1:10:1；[(dppv)FeS3CO]与[NaBF4]、[(dppe)NiCl2]之间的摩尔量比为1:10:1；[(dppv)FeS3CO]与[NaBF4]、[(dppv)NiCl2]之间的摩尔量比为1:10:1；[(dppv)FeS3CO]与[NaBF4]、[(dppp)NiCl2]之间的摩尔量比为1:10:1；[(dppv)FeS3CO]与[NaBF4]、[(dppb)NiCl2]之间的摩尔量比为1:10:1。
本发明的有益效果是:用此方法制备模型物的反应条件温和、工艺简单、原料廉价易得、收率较高，可制备多种含双膦配体和桥连三硫配体双(硫乙基)硫醚的[NiFe]氢化酶模型物。
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：
一种含双膦配体和桥连三硫配体双(硫乙基)硫醚的[NiFe]氢化酶模型物1的合成方法，所述模型物的化学式为[(dppe)Ni(μ-SCH2CH2)2SFe(dppe)][BF4]2，具体制备步骤如下：
1)在氮气保护下，向带有磁子的100mL Schlenk反应瓶中加入253.62mg(0.4mmol)化合物[(dppe)FeS3CO]；
2)向上述反应瓶中加入439.16mg(4mmol)[NaBF4]和210.40mg(0.4mmol)[(dppe)NiCl2]；
3)向上述反应中加入20mL丙酮，搅拌的混合溶液，于室温下反应6h，得到反应液；
4)将上述反应液减压抽干，用体积比为12:1的二氯甲烷-丙酮混合液作为展开剂进行薄层色谱分离，收集主色带，减压抽干得280.0mg橙黄色固体，产率55％。产物结构数据表征如下：IR(KBr disk):νC≡O:1980(s)cm-1.1HNMR(400MHz,CD3CN):8.01-7.72(m,40H,8C6H5),3.93-2.09(m,16H,SCH2CH2SCH2CH2S,2PCH2CH2P)ppm,31P NMR(161.9MHz,CD3CN):69.97(s),65.31(s)(Fe-P),49.49(s),41.75(s)(Ni-P)ppm.13C NMR(100MHz,CD3CN):210.56-210.29(m,CO),135.57-118.26(m,8C6H5)43.54-41.68,36.58-29.75,27.19-25.42,23.90-23.46(m,SCH2CH2SCH2CH2S,2PCH2CH2P)ppm.
实施例2：
一种含双膦配体和桥连三硫配体双(硫乙基)硫醚的[NiFe]氢化酶模型物2的合成方法，所述模型物的化学式为[(dppv)Ni(μ-SCH2CH2)2SFe(dppe)][BF4]2，具体制备步骤如下：
1)在氮气保护下，向带有磁子的100mL Schlenk反应瓶中加入253.62mg(0.4mmol)的[(dppe)FeS3CO]；
2)向上述反应瓶中加入439.16mg(4mmol)[NaBF4]和209.60mg(0.4mmol)[(dppv)NiCl2]；
3)向上述反应中加入20mL丙酮，搅拌的混合溶液，于室温下反应6h，得到反应液；
4)将上述反应液减压抽干，用体积比为12:1的二氯甲烷-丙酮混合液作为展开剂进行薄层色谱分离，收集主色带，减压抽干得309.8mg橙黄色固体，产率61％。产物结构数据表征如下：IR(KBr disk):νC≡O:1981(s)cm-1.1HNMR(400MHz,CD3CN):8.01-7.97(m,2H,PCH＝CHP),7.85-7.20,6.62-6.43(m,40H,8C6H5),3.89-3.84,3.54-3.40,3.22-3.20,2.56-2.50,2.31-2.12(m,12H,SCH2CH2SCH2CH2S,PCH2CH2P)ppm,31P NMR(161.9MHz,CD3CN):70.35(s),63.96(s),62.48(s)(Fe-P),53.74(s),50.79(s)(Ni-P)ppm.13C NMR(100MHz,CD3CN):210.68-210.36(m,CO),148.68-147.96,145.18-144.46(m,PCH＝CHP),135.07-118.26(m,8C6H5),43.47-41.87,31.72-31.63,29.37-29.55,28.92-27.77,25.88-25.49(m,SCH2CH2SCH2CH2S,PCH2CH2P)ppm.
实施例3：
一种含双膦配体和桥连三硫配体双(硫乙基)硫醚的[NiFe]氢化酶模型物3的合成方法，所述模型物的化学式为[(dppp)Ni(μ-SCH2CH2)2SFe(dppe)][BF4]2，具体制备步骤如下：
1)在氮气保护下，向带有磁子的100mL Schlenk反应瓶中加入253.62mg(0.4mmol)的[(dppe)FeS3CO]；
2)向上述反应瓶中加入439.16mg(4mmol)[NaBF4]和216.00mg(0.4mmol)[(dppp)NiCl2]；
3)向上述反应中加入20mL丙酮，搅拌的混合溶液，于室温下反应6h，得到反应液；
4)将上述反应液减压抽干，用体积比为12:1的二氯甲烷-丙酮混合液作为展开剂进行薄层色谱分离，收集主色带，减压抽干得351.1mg黑红色固体，产率67％。产物结构数据表征如下：IR(KBr disk):νC≡O:1965(s)cm-1.1HNMR(400MHz,CD3CN):8.23-6.32(m,40H,8C6H5),4.08-3.55,3.14-2.74,2.49-2.21,2.15-2.12(m,18H,SCH2CH2SCH2CH2S,PCH2CH2CH2P,PCH2CH2P)ppm,31PNMR(161.9MHz,CD3CN):69.23(s),62.69(s)(Fe-P),8.35(s),6.37(s)(Ni-P)ppm.13C NMR(100MHz,CD3CN):210.44-209.94(m,CO),136.95-118.26(m,8C6H5),42.94-42.54,35.53-32.85,28.79-25.76,24.89-24.11,18.18(m,SCH2CH2SCH2CH2S,PCH2CH2CH2P,PCH2CH2P)ppm.
实施例4：
一种含双膦配体和桥连三硫配体双(硫乙基)硫醚的[NiFe]氢化酶模型物4的合成方法，所述模型物的化学式为[(dppb)Ni(μ-SCH2CH2)2SFe(dppe)][BF4]2，具体制备步骤如下：
1)在氮气保护下，向带有磁子的100mL Schlenk反应瓶中加入253.62mg(0.4mmol)的[(dppe)FeS3CO]；
2)向上述反应瓶中加入439.16mg(4mmol)[NaBF4]和221.62mg(0.4mmol)[(dppb)NiCl2]；
3)向上述反应中加入20mL丙酮，搅拌的混合溶液，于室温下反应6h，得到反应液；
4)将上述反应液减压抽干，用体积比为12:1的二氯甲烷-丙酮混合液作为展开剂进行薄层色谱分离，收集主色带，减压抽干得188mg红色固体，产率36％。产物结构数据表征如下：IR(KBr disk):νC≡O:1953(s)cm-1.1HNMR(400MHz,CD3CN):8.18-6.95(m,40H,8C6H5),4.51-2.08(m,20H,SCH2CH2SCH2CH2S,PCH2CH2CH2CH2P,PCH2CH2P)ppm,31P NMR(161.9MHz,CD3CN):70.67(s),69.54(s),64.87(s),62.70(s)(Fe-P),13.24(s),12.63(s),10.02(s)(Ni-P)ppm.13C NMR(100MHz,CD3CN):211.57-210.75(m,CO),135.29-118.26(m,8C6H5),43.99-43.02,32.84-32.35,30.68-30.01,27.87-27.31,26.37-24.86(m,SCH2CH2SCH2CH2S,PCH2CH2CH2CH2P,PCH2CH2P)ppm.
实施例5：
一种含双膦配体和桥连三硫配体双(硫乙基)硫醚的[NiFe]氢化酶模型物5的合成方法，所述模型物的化学式为[(dppe)Ni(μ-SCH2CH2)2SFe(dppv)][BF4]2，具体制备步骤如下：
1)在氮气保护下，向带有磁子的100mL Schlenk反应瓶中加入252.81mg(0.4mmol)的[(dppv)FeS3CO]；
2)向上述反应瓶中加入439.16mg(4mmol)[NaBF4]和210.40mg(0.4mmol)[(dppe)NiCl2]；
3)向上述反应中加入20mL丙酮，搅拌的混合溶液，于室温下反应6h，得到反应液；
4)将上述反应液减压抽干，用体积比为12:1的二氯甲烷-丙酮混合液作为展开剂进行薄层色谱分离，收集主色带，减压抽干得340.2mg棕红色固体，产率67％。产物结构数据表征如下：IR(KBr disk):νC≡O:1976(s)cm-1.1HNMR(400MHz,CD3CN):8.35-8.21(m,2H,PCH＝CHP),8.19-6.75(m,40H,8C6H5),3.93-3.91,3.62-3.60,3.11-3.04,2.59-2.51,2.18(m,12H,PCH2CH2P,SCH2CH2SCH2CH2S)ppm,31P NMR(161.9MHz,CD3CN):78.94(s),76.79(s)(Fe-P),48.97(s),40.45(s)(Ni-P)ppm.13C NMR(100MHz,CD3CN):209.34-208.96(m,CO),150.99-148.93(m,PCH＝CHP),134.91-118.26(m,8C6H5),43.84-41.31,32.68-29.63,28.00-26.92,24.02-23.71(m,SCH2CH2SCH2CH2S,PCH2CH2P)ppm.
实施例6：
一种含双膦配体和桥连三硫配体双(硫乙基)硫醚的[NiFe]氢化酶模型物6的合成方法，所述模型物的化学式为[(dppv)Ni(μ-SCH2CH2)2SFe(dppv)][BF4]2，具体制备步骤如下：
1)在氮气保护下，向带有磁子的100mL Schlenk反应瓶中加入252.81mg(0.4mmol)的[(dppv)FeS3CO]；
2)向上述反应瓶中加入439.16mg(4mmol)[NaBF4]和209.60mg(0.4mmol)[(dppv)NiCl2]；
3)向上述反应中加入20mL丙酮，搅拌的混合溶液，于室温下反应6h，得到反应液；
4)将上述反应液减压抽干，用体积比为12:1的二氯甲烷-丙酮混合液作为展开剂进行薄层色谱分离，收集主色带，减压抽干得311.8mg红色固体，产率62％。产物结构数据表征如下：IR(KBr disk):νC≡O:1973(s)cm-1.1HNMR(400MHz,CD3CN):8.17-8.03(m,4H,2PCH＝CHP),7.93-7.21(m,40H,8C6H5),3.28-3.26,2.65-2.63,2.16,(m,8H,SCH2CH2SCH2CH2S)ppm,31P NMR(161.9MHz,CD3CN):66.75(s,Fe-P),55.09(s,Ni-P)ppm.13C NMR(100MHz,CD3CN):2117.30-216.88(m,CO),151.16-144.18(m,PCH＝CHP),134.75-118.26(m,8C6H5),43.78-41.23,31.89-30.23,29.72-27.90(m,SCH2CH2SCH2CH2S)ppm.
实施例7：
一种含双膦配体和桥连三硫配体双(硫乙基)硫醚的[NiFe]氢化酶模型物7的合成方法，所述模型物的化学式为[(dppp)Ni(μ-SCH2CH2)2SFe(dppv)][BF4]2，具体制备步骤如下：
1)在氮气保护下，向带有磁子的100mL Schlenk反应瓶中加入252.81mg(0.4mmol)的[(dppv)FeS3CO]；
2)向上述反应瓶中加入439.16mg(4mmol)[NaBF4]和216.00mg(0.4mmol)[(dppp)NiCl2]；
3)向上述反应中加入20mL丙酮，搅拌的混合溶液，于室温下反应6h，得到反应液；
4)将上述反应液减压抽干，用体积比为12:1的二氯甲烷-丙酮混合液作为展开剂进行薄层色谱分离，收集主色带，减压抽干得320.2mg红色固体，产率62％。产物结构数据表征如下：IR(KBr disk):νC≡O:1972(s)cm-1.1HNMR(400MHz,CD3CN):8.20-8.05(m,2H,PCH＝CHP),7.79-6.34(m,40H,8C6H5),4.07-4.04,3.77-3.55,3.16-3.10,2.91-2.72,(m,8H,SCH2CH2SCH2CH2S),2.52-2.49,2.15(m,6H,PCH2CH2CH2P)ppm,31P NMR(161.9MHz,CD3CN):78.03(s),74.91(s)(Fe-P),7.43(s,Ni-P)ppm.13C NMR(100MHz,CD3CN):208.74(m,CO),150.81-149.39(m,PCH＝CHP),135.23-118.26(m,8C6H5),43.46-43.26,62.56-29.56,25.26-24.22,18.22(m,SCH2CH2SCH2CH2S,PCH2CH2CH2P)ppm.
实施例8：
一种含双膦配体和桥连三硫配体双(硫乙基)硫醚的[NiFe]氢化酶模型物8的合成方法，所述模型物的化学式为[(dppb)Ni(μ-SCH2CH2)2SFe(dppv)][BF4]2，具体制备步骤如下：
1)在氮气保护下，向带有磁子的100mL Schlenk反应瓶中加入252.81mg(0.4mmol)的[(dppv)FeS3CO]；
2)向上述反应瓶中加入439.16mg(4mmol)[NaBF4]和221.62mg(0.4mmol)[(dppb)NiCl2]；
3)向上述反应中加入20mL丙酮，搅拌的混合溶液，于室温下反应6h，得到反应液；
4)将上述反应液减压抽干，用体积比为12:1的二氯甲烷-丙酮混合液作为展开剂进行薄层色谱分离，收集主色带，减压抽干得247.2mg红色固体，产率48％。产物结构数据表征如下：IR(KBr disk):νC≡O:1971(s)cm-1.1HNMR(400MHz,CD3CN):8.20-8.03(m,2H,PCH＝CHP),7.92-7.10(m,40H,8C6H5),3.93-3.88,3.55-3.46,3.36-3.33,3.12-3.06(m,8 H,SCH2CH2SCH2CH2S),2.13-2.02(m,8H,PCH2CH2CH2CH2P)ppm,31P NMR(161.9 MHz,CD3CN):78.20(s,Fe-P),73.54(s,Ni-P)ppm.13C NMR(100 MHz,CD3CN):209.46-208.74(m,CO),151.61-149.49(m,PCH＝CHP),134.83-118.26(m,8C6H5),55.26,46.38-46.00,44.08-44.14,32.66-32.24,30.90-23.23(m,SCH2CH2SCH2CH2S,PCH2CH2CH2CH2P)ppm。
Claims (4)
1.含双膦配体和桥连三硫配体双(硫乙基)硫醚[NiFe]氢化酶模型物，其特征是这种模型物使用[BF4 -]作为阴离子，而且模型物的铁中心只有一个羰基，
化学结构式如下所示：
结构式中L1,L2为[(dppe)＝1,2-双(二苯基膦)乙烷]或[(dppv)＝1,2-双(二苯基膦)乙烯]或[(dppp)＝1,3-双(二苯基膦)丙烷]或[(dppb)＝1,4-双(二苯基膦)丁烷]。
2.含双膦配体和桥连三硫配体双(硫乙基)硫醚[NiFe]氢化酶模型物合成方法，其特征是步骤如下：
1)在手套箱称取[FeCl2]于一个三口烧瓶中，氮气保护下，加入除氧的丙酮，通入CO，得淡黄色悬浮液，称取[dppe]或者[dppv]溶于除水除氧的四氢呋喃，室温下搅拌，溶液变为红色；
2)另称取氢化钠加入到一个反应瓶中，加入除水除氧的四氢呋喃，滴加双(巯乙基)硫醚，反应4h后，加入到上述溶液中，搅拌得反应液；
3)反应结束后，过滤，抽干溶剂得红色固体[(dppe)FeS3CO]或暗红色固体[(dppv)FeS3CO]；
4)在装有磁子的Schlenk反应瓶中，在氮气保护下加入[(dppe)FeS3CO]或者[(dppv)FeS3CO]；
5)向上述反应瓶中加入[NaBF4]，[(dppe)NiCl2]或者[(dppv)NiCl2]或者[(dppp)NiCl2]或者[(dppb)NiCl2]；
6)向上述反应瓶中加入丙酮，搅拌得到混合液，在室温下反应6h，得到反应液；
7)将上述反应液减压抽干，用体积比为12:1的二氯甲烷-丙酮混合液作为展开剂进行薄层色谱分离，收集主色带，减压抽干得到橙黄色物质即为含双(硫乙基)硫醚[NiFe]类氢化酶模型物1或5。
3.根据权利要求2所述的含双膦配体和桥连三硫配体双(硫乙基)硫醚[NiFe]氢化酶模型物合成方法，其特征是：所述步骤2)中[FeCl2],[dppe],[NaH]和双(巯乙基)硫醚之间的摩尔量比为1:1:3:1。
4.根据权利要求2所述的含双膦配体和桥连三硫配体双(硫乙基)硫醚[NiFe]氢化酶模型物合成方法，其特征是：所述步骤5)中[(dppe)FeS3CO]与[NaBF4]、[(dppe)NiCl2]之间的摩尔量比为1:10:1；[(dppe)FeS3CO]与[NaBF4]、[(dppv)NiCl2]之间的摩尔量比为1:10:1；[(dppe)FeS3CO]与[NaBF4]、[(dppp)NiCl2]之间的摩尔量比为1:10:1；[(dppe)FeS3CO]与[NaBF4]、[(dppb)NiCl2]之间的摩尔量比为1:10:1；[(dppv)FeS3CO]与[NaBF4]、[(dppe)NiCl2]之间的摩尔量比为1:10:1；[(dppv)FeS3CO]与[NaBF4]、[(dppv)NiCl2]之间的摩尔量比为1:10:1；[(dppv)FeS3CO]与[NaBF4]、[(dppp)NiCl2]之间的摩尔量比为1:10:1；[(dppv)FeS3CO]与[NaBF4]、[(dppb)NiCl2]之间的摩尔量比为1:10:1。
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