CN108558955A - 一种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物及其合成方法 - Google Patents
一种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物及其合成方法 Download PDFInfo
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- 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
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- 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
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Abstract
一种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物及其合成方法，所得化学结构式如下所示：在上述结构式中，缺少R1或R1为CH＝CH；R2为CH＝CH、CH2‑CH2或CH2‑CH2‑CH2；X为Cl或Br。本发明的优点是：本发明方法制备的含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物，原料廉价易得、反应条件温和、操作简单并且收率较高，适合于多种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物，并且该类模型物由于含共轭体系，可以很好地调节Ni原子周围的电子云密度，有利于催化剂在催化循环中的变价行为，具有潜在的优良催化质子还原产氢和异裂氢气的功能。
Description
技术领域
本发明属于金属有机、能源和材料科学领域，特别是含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物及其合成方法。
背景技术
随着社会的不断发展和进步，人类对能源的需求也越来越大，而传统能源的大量使用导致了环境污染和能源短缺等严重问题。氢气作为一种清洁、可再生能源引起了科学家们的广泛关注，但是将氢气作为一种常规能源还面临着许多技术问题，例如生产过程能耗高以及需用稀有贵金属铂催化剂等问题。而镍铁氢化酶是一类含地球上大量存在的贱金属镍和铁的生物酶，它可在温和的条件下高效地催化水中的质子产氢。因此人们希望通过这类酶的仿生化学研究以便合成一种人工酶催化产氢催化剂，从而可使氢气大规模生产和广泛使用(Vignais,P.M.；Billoud,B.；Meyer,J.FEMS Microbiol.Rev.2001,25,455-501；Song,L.–C.Acc.Chem.Res.2005,38,21-28；Lubitz,W.；Reijerse,E.；van Gastel,M.Chem.Rev.2007,107,4331-4365；Schilter,D.；Camara,J.M.；Huynh,M.T.；Hammes-Schiffer,S.；Rauchfuss,T.B.Chem.Rev.2016,116,8693-8749；S.Ogo.Coordin.Chem.Rev.2017,334,43)。
迄今为止，科学家们通过镍铁氢化酶的仿生化学研究，合成了一系列的镍铁氢化酶模型物，其中一些模型物具有良好的催化质子还原生成氢气或裂解氢气的功能(Barton,B.E.；Rauchfuss,T.B.J.Am.Chem.Soc.2010,132,14877-14885；Carroll,M.E.；Barton,B.E.；Gray,D.L.；Mack,A.E.；Rauchfuss,T.B.Inorg.Chem.2011,50,9554-9563；Ding,S.；Ghosh,P.；Lunsford,A.M.；Wang,N.；Bhuvanesh,N.；Hall,M.B.；Darensbourg,M.Y.J.Am.Chem.Soc.2016,138,12920-12927；Song,L.-C.；Han,X.F.；Chen,W.；Li,J.P.；Wang,Y.X.Dalton Trans.2017,46,10003-10013.Ogo,S.；Kabe,R.；Uehara,K.；Kure,B.；Nishimura,T.；Menon,S.；Harada,R.；Fukuzumi,S.；Higuchi,Y.；Tamada,T.；Kuroki,R.Scinece 2007,316,585-587；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；Song,L.-C.；Yang,X.-Y.；Cao,M.；Gao,X.-Y.；Liu,B.-B.；Zhu,L.；Jiang,F.Chem.Commun.2017,53,3818-3821)。
发明内容
针对上述技术分析，为了进一步发展镍铁氢化酶仿生化学，本发明的目的之一是利用含芳香性双氮配体的镍前体与含丙二硫桥的双膦铁前体反应合成了一类含共轭双氮配体及丙二硫桥配体的新型镍铁氢化酶模型物。
同时本发明还提供了含共轭双氮配体及丙二硫桥配体的新型镍铁氢化酶模型物的合成方法，该方法合成模型物的原料廉价、制备步骤简便、反应条件温和并且产率高，可用来制备多种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物。
本发明所得模型物既包含了具有平面结构的共轭双氮配体，又包含了镍铁之间的丙二硫桥结构，对于研发价格低廉、催化性能优良的人工酶催化剂具有应用价值。同时该类模型物在催化质子产氢和裂解氢气方面具有潜在的应用价值。
为了达到上述目的，本发明的技术方案是：
一种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物，其化学结构式如下所示：
在上述结构式中，缺少R1或R1为CH＝CH；R2为CH＝CH、CH2-CH2或CH2-CH2-CH2；X为Cl或Br。
一种所述含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物的合成方法，步骤如下：
1)氮气保护下，将装有含共轭双氮配体的镍前体(N2NiX2)、含丙撑桥及双膦配体的铁前体和KPF6的反应瓶中加入无水丙酮混合，在室温下搅拌均匀并反应，反应完毕后得到反应液；
2)将上述反应液用真空泵减压抽干溶剂，残留物用适量二氯甲烷提取，然后用二氯甲烷/丙酮为展开剂进行硅胶柱色谱分离，收集棕红色主带，然后将收集液用真空泵减压抽干溶剂，得到固体即为目标产物。
所述步骤1)中镍前体：铁前体：KPF6的用量比例为1mmol:1mmol:5mmol，加入丙酮后室温搅拌反应5-6小时。
所述步骤2)中二氯甲烷/丙酮的体积比为15mL:1mL，硅胶柱长度为10-15cm。
本发明的有益效果是：利用该方法制备含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物，原料廉价易得、反应条件温和、操作简单并且收率较高，适合于多种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物，并且该类模型物由于含共轭体系，可以很好地调节Ni原子周围的电子云密度，有利于催化剂在催化循环中的变价行为，具有潜在的优良催化质子产氢和裂解氢气的能力。
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：
一种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物1的制备方法，所述模型物的化学式为[(phen)Ni(pdt)(μ-Cl)Fe(CO)(dppv)](PF6)[phen＝1,10-邻菲啰啉，dppv＝顺-1,2-双(二苯基膦)乙烯]，制备过程如下所示：
具体制备步骤如下：
1)氮气保护下，将装有310mg(1.0mmol)(phen)NiCl2、615mg(1.0mmol)(dppv)Fe(CO)2(pdt)和920mg KPF6的100mL Schlenk反应瓶中加入无水除氧丙酮40mL，室温下搅拌，红色悬浊液逐渐变为红棕色，反应5小时后得到反应液；
2)将上述反应液用真空泵减压抽干溶剂，残留物用适量二氯甲烷提取，然后用二氯甲烷/丙酮＝15:1(v/v)作为展开剂进行硅胶柱色谱分离，收集棕红色主带，然后用真空泵减压抽干溶剂，得到755mg的棕红色固体1，产率75％。
产物结构数据表征如下：Anal.Calcd for C42H36ClF6FeN2NiOP3S2:C,50.16；H,3.61；N,2.79.Found:C,50.01；H,3.89；N,2.66.IR(KBr disk):νC≡O:1942(s)cm-1.1H NMR(400MHz,acetone-d6):2.67-5.18(m，6H，CH2CH2CH2),7.37-7.87(m，20H，4C6H5),8.25-10.69(m，10H，C12H8N2，CH＝CH)ppm.13C NMR(100MHz,CD2Cl2):26.2，29.8，40.1(s，SCH2CH2CH2S),126.5-146.5(m，C6H5，C12H8N2),148.3-149.1(m，CH＝CH),217.3(s，CO)ppm.31P NMR(162MHz,acetone-d6):78.6(s，Fe-P),-153.0—-135.5(m，PF6)ppm.
实施例2：
一种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物2的制备方法，所述模型物的化学式为[(phen)Ni(pdt)(μ-Cl)Fe(CO)(dppe)](PF6)[phen＝1,10-邻菲啰啉，dppe＝1,2-双(二苯基膦)乙烷]，制备过程如下所示：
具体制备步骤如下：
1)氮气保护下，将装有310mg(1.0mmol)(phen)NiCl2、616mg(1.0mmol)(dppe)Fe(CO)2(pdt)和920mg KPF6的100mL Schlenk反应瓶中加入无水除氧丙酮40mL，室温下搅拌，红色悬浊液逐渐变为红棕色，反应5小时后得到反应液；
2)将上述反应液用真空泵减压抽干溶剂，残留物用适量二氯甲烷提取，然后用二氯甲烷/丙酮＝15:1(v/v)作为展开剂进行硅胶柱色谱分离，收集棕红色主带，然后用真空泵减压抽干溶剂，得到716mg的棕红色固体2，产率71％。
产物结构数据表征如下：Anal.Calcd for C42H38ClF6FeN2NiOP3S2:C,50.06；H,3.80；N,2.78.Found:C,50.14；H,4.01；N,2.71.IR(KBr disk):νC≡O:1935(s)cm-1.1H NMR(400MHz,acetone-d6):2.88-4.09(m，10H，SCH2CH2CH2S，PCH2CH2P),7.33-7.92(m，20H，4C6H5),8.23-9.71(m，8H，C12H8N2)ppm.13C NMR(100MHz,CD3CN):24.6-25.0(m，PCH2CH2P),30.2，44.3(s，SCH2CH2CH2S),128.3-145.6(m，C6H5，C12H8N2),223.9(s，CO)ppm.31P NMR(162MHz,acetone-d6):67.8(s，Fe-P),-153.0—-135.5(m，PF6)ppm.
实施例3：
一种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物3的制备方法，所述模型物的化学式为[(phen)Ni(pdt)(μ-Cl)Fe(CO)(dppp)](PF6)[phen＝1,10-邻菲啰啉，dppp＝1,3-双(二苯基膦)丙烷]，制备过程如下所示：
具体制备步骤如下：
1)氮气保护下，将装有310mg(1.0mmol)(phen)NiCl2、630mg(1.0mmol)(dppp)Fe(CO)2(pdt)和920mg KPF6的100mL Schlenk反应瓶中加入无水除氧丙酮40mL，室温下搅拌，红色悬浊液逐渐变为红棕色，反应5小时后得到反应液；
2)将上述反应液用真空泵减压抽干溶剂，残留物用适量二氯甲烷提取，然后用二氯甲烷/丙酮＝15:1(v/v)作为展开剂进行硅胶柱色谱分离，收集棕红色主带，然后用真空泵减压抽干溶剂，得到736mg的棕红色固体3，产率72％。
产物结构数据表征如下：Anal.Calcd for C43H40ClF6FeN2NiOP3S2:C,50.54；H,3.95；N,2.74.Found:C,50.27；H,3.92；N,2.67.IR(KBr disk):νC≡O:1928(s)cm-1.1H NMR(400MHz,acetone-d6):1.61-1.72,2.10-2.41,3.18-3.81(3m，12H，SCH2CH2CH2S，PCH2CH2CH2P),7.41-7.92(m，20H，4C6H5),7.97-8.89(m，8H，C12H8N2)ppm.13C NMR(100MHz,CD2Cl2):18.8-25.1(m，PCH2CH2CH2P),26.7，38.7(s，SCH2CH2CH2S),125.7-149.6(m，C6H5，C12H8N2),220.0-220.4(m，CO)ppm.31P NMR(162MHz,acetone-d6):42.0(s，Fe-P),-153.0—-135.5(m，PF6)ppm.
实施例4：
一种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物4的制备方法，所述模型物的化学式为[(bpy)Ni(pdt)(μ-Br)Fe(CO)(dppv)](PF6)[bpy＝2,2’-联吡啶，dppv＝顺-1,2-双(二苯基膦)乙烯]，制备过程如下所示：
具体制备步骤如下：
1)氮气保护下，将装有375mg(1.0mmol)(bpy)NiCl2、615mg(1.0mmol)(dppv)Fe(CO)2(pdt)和920mg KPF6的100mL Schlenk反应瓶中加入无水除氧丙酮40mL，室温下搅拌，红色悬浊液逐渐变为红棕色，反应5小时后得到反应液；
2)将上述反应液用真空泵减压抽干溶剂，残留物用适量二氯甲烷提取，然后用二氯甲烷/丙酮＝15:1(v/v)作为展开剂进行硅胶柱色谱分离，收集棕红色主带，然后用真空泵减压抽干溶剂，得到739mg的红棕色固体4，产率72％。
产物结构数据表征如下：Anal.Calcd for C40H36BrF6FeN2NiOP3S2:C,46.82；H,3.54；N,2.73.Found:C,47.07；H,3.49；N,2.77.IR(KBr disk):νC≡O:1944(s)cm-1.1H NMR(400MHz,acetone-d6):2.26-2.81,3.07-4.24(2m，6H，CH2CH2CH2),7.39-8.93(m，30H，4C6H5，C10H8N2，CH＝CH)ppm.13C NMR(100MHz,CD3CN):27.5,38.7(s，SCH2CH2CH2S),123.3-153.9(m，C6H5，C10H8N2，CH＝CH),219.7(s，CO)ppm.31P NMR(162MHz,acetone-d6):71.8(s，Fe-P),-153.0—-135.5(m，PF6)ppm.
实施例5：
一种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物5的制备方法，所述模型物的化学式为[(bpy)Ni(pdt)(μ-Br)Fe(CO)(dppe)](PF6)[bpy＝2,2’-联吡啶，dppe＝1,2-双(二苯基膦)乙烷]，制备过程如下所示：
具体制备步骤如下：
1)氮气保护下，将装有375mg(1.0mmol)(bpy)NiCl2、616mg(1.0mmol)(dppe)Fe(CO)2(pdt)和920mg KPF6的100mL Schlenk反应瓶中加入无水除氧丙酮40mL，室温下搅拌，红色悬浊液逐渐变为红棕色，反应6小时后得到反应液；
2)将上述反应液用真空泵减压抽干溶剂，残留物用适量二氯甲烷提取，然后用二氯甲烷/丙酮＝15:1(v/v)作为展开剂进行硅胶柱色谱分离，收集棕红色主带，然后用真空泵减压抽干溶剂，得到750mg的红棕色固体5，产率73％。
产物结构数据表征如下：Anal.Calcd for C40H38BrF6FeN2NiOP3S2:C,46.72；H,3.73；N,2.72.Found:C,46.72；H,3.87；N,2.46.IR(KBr disk):νC≡O:1936(s)cm-1.1H NMR(400MHz,acetone-d6):2.38-2.44，2.94-3.41，4.24-4.28(3m，10H，SCH2CH2CH2S，PCH2CH2P),7.33-8.94(m，28H，4C6H5，C10H8N2)ppm.13C NMR(100MHz,CD3CN):24.5-24.9(m，PCH2CH2P),28.1,38.7(s，SCH2CH2CH2S),127.7-154.3(m，C6H5，C10H8N2),220.5-221.0(m，CO)ppm.31P NMR(162MHz,acetone-d6):62.6(s，Fe-P),-153.0—-135.5(m，PF6)ppm.
实施例6：
一种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物6的制备方法，所述模型物的化学式为[(bpy)Ni(pdt)(μ-Br)Fe(CO)(dppp)](PF6)[bpy＝2,2’-联吡啶，dppp＝1,3-双(二苯基膦)丙烷]，制备过程如下所示：
具体制备步骤如下：
1)氮气保护下，将装有375mg(1.0mmol)(bpy)NiCl2、630mg(1.0mmol)(dppp)Fe(CO)2(pdt)和920mg KPF6的100mL Schlenk反应瓶中加入无水除氧丙酮40mL，室温下搅拌，红色悬浊液逐渐变为红棕色，反应6小时后得到反应液；
2)将上述反应液用真空泵减压抽干溶剂，残留物用适量二氯甲烷提取，然后用二氯甲烷/丙酮＝15:1(v/v)作为展开剂进行硅胶柱色谱分离，收集棕红色主带，然后用真空泵减压抽干溶剂，得到698mg的红棕色固体6，产率67％。
产物结构数据表征如下：Anal.Calcd for C41H40BrF6FeN2NiOP3S2:C,47.25；H,3.87；N,2.69.Found:C,47.50；H,3.81；N,2.54.IR(KBr disk):νC≡O:1924(s)cm-1.1H NMR(400MHz,acetone-d6):1.66-1.70,2.21-2.60,3.36-3.43,3.79-3.82(4m,12H,SCH2CH2CH2S,PCH2CH2CH2P),7.41-8.39(m，28H，4C6H5，C10H8N2)ppm.13C NMR(100MHz,CD3CN):19.0-25.6(m，PCH2CH2CH2P),27.5，38.2(s，SCH2CH2CH2S),123.0-154.7(m，C6H5，C10H8N2),222.7(s，CO)ppm.31P NMR(162MHz,acetone-d6):42.0(s，Fe-P),-153.0—-135.5(m，PF6)ppm。
Claims (4)
1.一种含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物，其化学结构式如下所示：
在上述结构式中，缺少R1或R1为CH＝CH；R2为CH＝CH、CH2-CH2或CH2-CH2-CH2；X为Cl或Br。
2.一种如权利要求1所述含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物的合成方法，其特征在于步骤如下：
1)氮气保护下，将装有含共轭双氮配体的镍前体(N2NiX2)、含丙撑桥及双膦配体的铁前体和KPF6的反应瓶中加入无水丙酮混合，在室温下搅拌均匀并反应，反应完毕后得到反应液；
2)将上述反应液用真空泵减压抽干溶剂，残留物用适量二氯甲烷提取，然后用二氯甲烷/丙酮为展开剂进行硅胶柱色谱分离，收集棕红色主带，然后将收集液用真空泵减压抽干溶剂，得到固体即为目标产物。
3.根据权利要求2所述含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物的合成方法，其特征在于：所述步骤1)中镍前体：铁前体：KPF6的用量比例为1mmol:1mmol:5mmol，加入丙酮后室温搅拌反应5-6小时。
4.根据权利要求2所述含共轭双氮配体及丙二硫桥的镍铁氢化酶模型物的合成方法，其特征在于：所述步骤2)中二氯甲烷/丙酮的体积比为15mL:1mL，硅胶柱长度为10-15cm。
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