CN106632512A - 一类含功能化膦配体的铁铁氢化酶模型物及其制备方法 - Google Patents
一类含功能化膦配体的铁铁氢化酶模型物及其制备方法 Download PDFInfo
- Publication number
- CN106632512A CN106632512A CN201610828784.6A CN201610828784A CN106632512A CN 106632512 A CN106632512 A CN 106632512A CN 201610828784 A CN201610828784 A CN 201610828784A CN 106632512 A CN106632512 A CN 106632512A
- Authority
- CN
- China
- Prior art keywords
- iron
- solvent
- phosphine ligands
- thing
- preparation
- 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
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003446 ligand Substances 0.000 title claims abstract description 36
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 26
- 229910017108 Fe—Fe Inorganic materials 0.000 title abstract 4
- 108010020056 Hydrogenase Proteins 0.000 title abstract 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 3
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims abstract 6
- NJFMNPFATSYWHB-UHFFFAOYSA-N ac1l9hgr Chemical compound [Fe].[Fe] NJFMNPFATSYWHB-UHFFFAOYSA-N 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- 238000007306 functionalization reaction Methods 0.000 claims description 22
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 9
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 235000019439 ethyl acetate Nutrition 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- XYBIRPPWHMBGJM-UHFFFAOYSA-N diphenylphosphane phenol Chemical compound Oc1ccccc1.P(c1ccccc1)c1ccccc1 XYBIRPPWHMBGJM-UHFFFAOYSA-N 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 238000001228 spectrum Methods 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 abstract 2
- QOPABJOZVXZFJG-UHFFFAOYSA-N 4-diphenylphosphanylphenol Chemical compound C1=CC(O)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QOPABJOZVXZFJG-UHFFFAOYSA-N 0.000 abstract 1
- WBTHXVQDYNENSM-UHFFFAOYSA-N C1(=CC=CC=C1)P.CCC(=O)O.CCC(=O)O Chemical compound C1(=CC=CC=C1)P.CCC(=O)O.CCC(=O)O WBTHXVQDYNENSM-UHFFFAOYSA-N 0.000 abstract 1
- LJDGKIUMGVMSGI-UHFFFAOYSA-N [hydroxymethyl(phenyl)phosphanyl]methanol Chemical compound OCP(CO)C1=CC=CC=C1 LJDGKIUMGVMSGI-UHFFFAOYSA-N 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000004809 thin layer chromatography Methods 0.000 description 10
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 9
- 239000007787 solid Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000004679 31P NMR spectroscopy Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000000547 structure data Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 101000905241 Mus musculus Heart- and neural crest derivatives-expressed protein 1 Proteins 0.000 description 3
- 101001031591 Mus musculus Heart- and neural crest derivatives-expressed protein 2 Proteins 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 108010072136 iron hydrogenase Proteins 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 methylols Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic 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
- C07F15/02—Iron 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一类含功能化膦配体的铁铁氢化酶模型物,该模型物中的[2Fe2S]催化中心连有亲水性基团功能化的膦配体,其化学结构式如下所示:结构式中:R为氢或羟甲基(CH2OH),L为双羟甲基苯膦[PhP(CH2OH)2]、羟甲基/乙酸甲酯基苯膦[PhP(CH2OH)(CH2CO2Me)]、双乙酸甲酯基苯膦[PhP(CH2CO2Me)2]或对羟基苯基二苯基膦[Ph2P(C6H4OH‑p)]。本发明的有益效果是:利用该方法制备含功能化膦配体的铁铁氢化酶模型物,原料易得、条件温和、操作简便,适合于多种功能化膦配体的铁铁氢化酶模型物的制备,并且该类模型物具有潜在的优良催化产氢能力。
Description
技术领域
本发明属于金属有机,能源和材料科学领域,特别是一类含功能化膦配体的铁铁氢化酶模型物及其制备方法。
背景技术
解决能源匮乏和环境污染是当今人类社会所面临的重大挑战之一。尽管氢气是一种具有高燃烧值和可再生的清洁燃料,但至今尚无一种基于廉价金属的高效催化剂,用它可以实现工业化催化水中的质子产生氢气。铁铁氢化酶是一种存在于微生物体内并能高效催化质子还原为氢气的金属酶。近年来,科学家们对铁铁氢化酶活性中心结构和功能模拟进行了广泛深入的研究,以期合成一种理想的“人工酶”产氢催化剂,参见:Darensbourg,M.Y.;Lyon,E.J.;Smee,J.J.Coord.Chem.Rev.2000,206-207,533-561;Frey,M.ChemBioChem 2002,3,153-160;Song,L.-C.Acc.Chem.Res.2005,38,21-28;Capton,J.-F.;Gloaguen,F.;Pétillon,F.Y.;Schollhammer,P.;Talarmin,J.Coord.Chem.Rev.2009,253,1476-1494;Lubitz,W.;Ogata,H.;Rüdiger,O.;Reijerse,E.Chem.Rev.2014,114,4081-4148。
为了研发廉价金属铁的高效“人工酶”产氢催化剂,人们已成功地将几种具有给电子能力的水溶性膦配体引入到[2Fe2S]子簇结构中,从而合成了几例含亲水性膦配体的铁铁氢化酶模型物。这些亲水性膦配体可以增加含[2Fe2S]子簇结构模型物在水中的溶解性,从而有效地提高其催化产氢功能,参见:Mejia-Rodiguez,R.;Chong,D.;Reibenspies,J.H.;Soriaga,M.P.;Darensbourg,M.Y.J.Am.Chem.Soc.2004,126,12004-12014;Vannucci,A.K.;Wang,S.;Nichol,G.S.;Lichtenberger,D.L.;Evans,D.H.;Glass,R.S.Dalton.Trans.2010,39,3050-3056;Roy,S.;Nguyen,T.-A.D.;Gan,L.;Jones,A.K.Dalton.Trans.2015,44,14865-14876。
鉴于到目前为止,含双羟甲基、羟甲基/乙酸甲酯基、双乙酸甲酯基及对羟基苯基功能化膦配体的铁铁氢化酶模型物尚未被合成,因此为了更好地提高铁铁氢化酶模型物的水溶性和催化产氢功能,我们通过羰基配体取代反应将上述含亲水性基团的膦配体引入到铁铁氢化酶模型物的[2Fe2S]催化中心骨架上,合成了一系列结构新颖并具有潜在优良催化产氢功能的铁铁氢化酶模型物。
发明内容
本发明的目的是针对上述技术分析,提供一类含功能化膦配体的铁铁氢化酶模型物及其制备方法,该类模型物中的[2Fe2S]催化中心连有亲水性基团功能化的膦配体;模型物合成方法简便、反应条件温和、易操作,可用来制备多种含功能化膦配体的铁铁氢化酶模型物。
本发明的技术方案:
一类含功能化膦配体的铁铁氢化酶模型物,该模型物中的[2Fe2S]催化中心连有亲水性基团功能化的膦配体,其化学结构式如下所示:
结构式中:R为氢或羟甲基(CH2OH),L为双羟甲基苯膦[PhP(CH2OH)2]、羟甲基/乙酸甲酯基苯膦[PhP(CH2OH)(CH2CO2Me)]、双乙酸甲酯基苯膦[PhP(CH2CO2Me)2]或对羟基苯基二苯基膦[Ph2P(C6H4OH-p)]。
一类所述含功能化膦配体的铁铁氢化酶模型物的制备方法,步骤如下:
1)氮气保护下,将[(μ-SCH2(CHR)CH2S-μ)]Fe2(CO)6和有机溶剂混合,然后加入膦配体,在室温下搅拌0.5-12h或加热回流30h,TLC检测原料基本反应完,得到初级产物;
2)将上述初级产物减压抽干溶剂,用有机溶剂提取残余物,然后用混合溶剂为展开剂进行薄层色谱分离,得到一级目标化合物。
3)氮气保护下,将丙二酸、4-二甲氨基吡啶(DMAP)和二环己基碳二亚胺(DCC)置于冰水浴降至0℃,加入CH2Cl2,搅拌2h后,一次性加入上述一级目标化合物,撤去冰水浴自然升至室温,继续搅拌6h,TLC监测原料点基本消失,得到二级产物;
4)将上述二级产物减压抽干,用CH2Cl2提取残余物,用混合溶剂作为展开剂进行薄层色谱分离,得二级目标化合物。
所述步骤1)中有机溶剂为四氢呋喃或MeCN,[(μ-SCH2(CHR)CH2S-μ)]Fe2(CO)6、有机溶剂与膦配体的用量比为1.0mmol:16-40mL:1.1-2.4mmol。
所述步骤2)中有机溶剂为EtOAc或CH2Cl2,混合溶剂为体积比为1:1-1.5的石油醚-EtOAc混合溶剂或体积比为1:2的石油醚-CH2Cl2混合溶剂。
所述步骤3)中丙二酸、4-二甲氨基吡啶(DMAP)、二环己基碳二亚胺(DCC)、CH2Cl2与一级目标化合物的用量比为0.46mmol:0.56mmol:1.06mmol:20mL:0.23-0.46mmol。
所述步骤4)中混合溶剂为体积比为2:3的石油醚-CH2Cl2混合溶剂。
本发明的有益效果是:利用该方法制备含功能化膦配体的铁铁氢化酶模型物,原料易得、条件温和、操作简便,适合于多种功能化膦配体的铁铁氢化酶模型物的制备,并且该类模型物具有潜在的优良催化产氢能力。
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:
一类含功能化膦配体的铁铁氢化酶模型物1的制备方法,所述模型物1的化学式为[{(μ-SCH2)2CH2}Fe2(CO)4][PhP(CH2OH)2]2,制备过程如下所示:
具体制备步骤如下:
1)在氮气保护下,向装有搅拌磁子的50mL Schlenk烧瓶中依次加入386mg(1.0mmol)[(μ-SCH2)2CH2]Fe2(CO)6和30mL四氢呋喃,得红棕色溶液;
2)在室温和氮气保护下,用一次性注射器将408mg(2.4mmol)PhP(CH2OH)2稠状物直接滴加到红棕色溶液中,加热回流30h,得黑红色溶液,TLC监测原料点基本消失;
3)减压抽干溶剂,用EtOAc提取残余物,用石油醚/EtOAc=1:1(v/v)作为展开剂进行薄层色谱分离,收集红棕色主色带,减压抽干得红棕色油状物,向其加入少量CH2Cl2后真空减压抽干,得到红棕色固体模型物1(135mg),产率20%。
产物结构数据表征如下:IR(KBr disk):νO-H:3311(m);νC≡O:1988(vs),1950(vs),1916(vs)cm-1.1H NMR(400MHz,CDCl3):1.41-1.64(m,6H,CH2CH2CH2),2.63(br.s,4H,4OH),4.61(br.s,8H,4CH2O),7.47,7.78(2br.s,10H,2C6H5)ppm.13C NMR(100MHz,CDCl3):22.5,30.0(2s,CH2CH2CH2),62.9,63.2(2s,CH2O),129.0-131.8(m,C6H5),214.5,214.6(2s,C≡O)ppm.31P NMR(162MHz,CDCl3):55.3(s)ppm.
实施例2:
一类含功能化膦配体的铁铁氢化酶模型物2的制备方法,所述模型物2的化学式为[{(μ-SCH2)2CHCH2OH}Fe2(CO)5][PhP(CH2OH)2],制备过程如下所示:
具体制备步骤如下:
1)在氮气保护下,向装有搅拌磁子的50mL Schlenk烧瓶中依次加入374mg(0.9mmol)[(μ-SCH2)2CHCH2OH]Fe2(CO)6和15mL四氢呋喃,得红色溶液;
2)在室温和氮气保护下,用一次性注射器将170mg(1.0mmol)PhP(CH2OH)2稠状物直接滴加到红色溶液中,室温搅拌过夜,得红棕色溶液,TLC监测有一明显的红色新点出现并有少量原料红点斑点存在;
3)减压抽干溶剂,用EtOAc提取残余物,用石油醚/EtOAc=2:3(v/v)作为展开剂进行薄层色谱分离,收集红色主色带,减压抽干得红色油状物,向其加入少量无水乙醚后真空减压抽干,得到红色固体模型物2(113mg),产率39%。(注:回收原料红色固体156mg)
产物结构数据表征如下:IR(KBr disk):νO-H:3448(m);νC≡O:2041(vs),1978(vs),1926(m)cm-1.1H NMR(400MHz,CD3COCD3):1.11-1.21(m,1H,CH2CHCH2),1.43(t,JHH=J'HH=12.8Hz,2H,2SCHeHa),2.42(dd,JHH=12.8Hz,J'HH=3.2Hz,2H,2SCHeHa),3.09(s,2H,CHCH2O),3.67(br.s,1H,CHCH2OH),4.59,4.70(2d,JHH=12.8Hz,4H,P(CH2O)2),4.85(br.s,2H,P(CH2OH)2),7.45-7.88(m,5H,C6H5)ppm.13C NMR(100MHz,CD3COCD3):27.2(s,SCH2),46.8(s,CH),62.1,62.5(2s,PCH2O),66.6(s,CHCH2O),129.2-134.1(m,C6H5),211.1,211.7,214.7,214.8(4s,C≡O)ppm.31PNMR(162MHz,CD3COCD3):56.3(s)ppm.
实施例3:
一类含功能化膦配体的铁铁氢化酶模型物3的制备方法,所述模型物3的化学式为[{(μ-SCH2)2CH2}Fe2(CO)5][PhP(CH2OH)(CH2CO2Me)],制备过程如下所示:
具体制备步骤如下:
1)在氮气保护下,向装有搅拌磁子的50mL Schlenk烧瓶中依次加入48mg(0.46mmol)CH2(CO2H)2、68mg(0.56mmol)DMAP和220mg(1.06mmol)DCC,将其置于冰水浴降至0℃,注入20mL CH2Cl2;
2)低温搅拌2h后,一次性加入243mg(0.46mmol)模型物 [{(μ-SCH2)2CH2}Fe2(CO)5][PhP(CH2OH)2],撤去冰水浴自然升至室温,继续搅拌6h,TLC监测原料点基本消失;
3)减压抽干溶剂,用CH2Cl2提取残余物,用石油醚/CH2Cl2=2:3(v/v)作为展开剂进行薄层色谱分离,收集红棕色主色带,减压抽干,得到红色固体模型物3(116mg),产率44%。
产物结构数据表征如下:IR(KBr disk):νO-H:3401(m);νC≡O:2047(vs),1976(vs),1957(vs),1935(vs);νC=O:1720(s)cm-1.1H NMR(400MHz,CDCl3):1.69-1.95(m,6H,CH2CH2CH2),2.18(s,3H,CH3),3.21(t,JHH=6.8Hz,1H,OH),4.37-4.59(m,2H,HOCH2P),4.67,5.24(2d,J=12.8Hz,2H,CH3CO2CH2P),7.45,7.73(2br.s,5H,C6H5)ppm.13C NMR(100MHz,CDCl3):19.6(s,CH3),22.0,22.2,29.2(3s,CH2CH2CH2),59.4,59.7,61.0,61.2(4s,PCH2O),127.9-130.6(m,C6H5),170.7(s,CH3CO2),208.5,211.9,212.0(3s,C≡O)ppm.31P NMR(162MHz,CDCl3):58.1(s)ppm.
实施例4:
一类含功能化膦配体的铁铁氢化酶模型物4的制备方法,所述模型物4的化学式为[{(μ-SCH2)2CH2}Fe2(CO)5][PhP(CH2CO2Me)2],制备过程如下所示:
具体制备步骤与实施例3基本相同,不同之处在于:步骤2)中将加入243mg(0.46mmol)[{(μ-SCH2)2CH2}Fe2(CO)5][PhP(CH2OH)2]改为加入122mg(0.23mmol)[{(μ-SCH2)2CH2}Fe2(CO)5][PhP(CH2OH)2];步骤3)中将收集红棕色主色带(Rf=0.1)改为收集橙红色主色带,得到红色固体模型物4(127mg),产率90%。
产物结构数据表征如下:IR(KBr disk):νC≡O:2045(vs),1983(vs),1933(s);νC=O:1752(s)cm-1.1H NMR(400MHz,CDCl3):1.70(s,2H,(CH2CH2CH2),1.89(s,4H,CH2CH2CH2),2.11(s,6H,CH3),4.87,5.02(2d,J=12.8Hz,4H,P(CH2O)2),7.45-7.63(m,5H,C6H5)ppm.13C NMR(100MHz,CDCl3):19.5(s,CH3),22.1,29.3(2s,CH2CH2CH2),59.7(s,PCH2O),127.9-130.2(m,C6H5),169.1,169.2(2s,CH3CO2),208.4,211.6,211.7(3s C≡O)ppm.31P NMR(162MHz,CDCl3):53.5(s)ppm.
实施例5:
一类含功能化膦配体的铁铁氢化酶模型物5的制备方法,所述模型物5的化学式为[{(μ-SCH2)2CH2}Fe2(CO)5][Ph2P(p-C6H4OH)],制备过程如下所示:
具体制备步骤如下:
1)在氮气保护下,向装有搅拌磁子的50mL Schlenk烧瓶中依次加入193mg(0.5mmol)[(μ-SCH2)2CH2]Fe2(CO)6、287mg(1.1mmol)Ph2P(p-C6H4OH)和20mLMeCN,搅拌使之完全溶解;
2)在室温和氮气保护下,一次性加入111mg(1.0mmol)Me3NO·2H2O,溶液颜色立即由红色变为黑红色,室温继续搅拌0.5h,TLC监测原料点完全消失;
3)减压抽干溶剂,用CH2Cl2提取残余物,用石油醚/CH2Cl2=1:2(v/v)作为展开剂进行薄层色谱分离,收集红棕色主色带,减压抽干得红色油状物,向其加入少量无水乙醚后真空减压抽干,得到红色固体模型物5(292mg),产率92%。
产物结构数据表征如下:IR(KBr disk):νO-H:3480(m);νC≡O:2043(vs),1979(vs),1931(m)cm-1.1H NMR(400MHz,CDCl3):1.10-1.74(m,6H,CH2CH2CH2),5.23(br.s,1H,OH),6.91-7.65(m,14H,2C6H5,C6H4)ppm.13C NMR(100MHz,CDCl3):22.0,29.9(2s,CH2CH2CH2),115.6-157.5(m,2C6H5,C6H4),209.6,213.6,213.7(3s,C≡O)ppm.31PNMR(162MHz,CDCl3):63.4(s)ppm。
Claims (6)
1.一类含功能化膦配体的铁铁氢化酶模型物,其特征在于该模型物中的[2Fe2S]催化中心连有亲水性基团功能化的膦配体,其化学结构式如下所示:
结构式中:R为氢或羟甲基(CH2OH),L为双羟甲基苯膦[PhP(CH2OH)2]、羟甲基/乙酸甲酯基苯膦[PhP(CH2OH)(CH2CO2Me)]、双乙酸甲酯基苯膦[PhP(CH2CO2Me)2]或对羟基苯基二苯基膦[Ph2P(C6H4OH-p)]。
2.一类如权利要求1所述含功能化膦配体的铁铁氢化酶模型物的制备方法,其特征在于步骤如下:
1)氮气保护下,将[(μ-SCH2(CHR)CH2S-μ)]Fe2(CO)6和有机溶剂混合,然后加入膦配体,在室温下搅拌0.5-12h或加热回流30h,TLC检测原料基本反应完,得到初级产物;
2)将上述初级产物减压抽干溶剂,用有机溶剂提取残余物,然后用混合溶剂为展开剂进行薄层色谱分离,得到一级目标化合物。
3)氮气保护下,将丙二酸、4-二甲氨基吡啶(DMAP)和二环己基碳二亚胺(DCC)置于冰水浴降至0℃,加入CH2Cl2,搅拌2h后,一次性加入上述一级目标化合物,撤去冰水浴自然升至室温,继续搅拌6h,TLC监测原料点基本消失,得到二级产物;
4)将上述二级产物减压抽干,用CH2Cl2提取残余物,用混合溶剂作为展开剂进行薄层色谱分离,得二级目标化合物。
3.根据权利要求2所述含功能化膦配体的铁铁氢化酶模型物的制备方法,其特征在于:所述步骤1)中有机溶剂为四氢呋喃或MeCN,[(μ-SCH2(CHR)CH2S-μ)]Fe2(CO)6、有机溶剂与膦配体的用量比为1.0mmol:16-40mL:1.1-2.4mmol。
4.根据权利要求2所述含功能化膦配体的铁铁氢化酶模型物的制备方法,其特征在于:所述步骤2)中有机溶剂为EtOAc或CH2Cl2,混合溶剂为体积比为1:1-1.5的石油醚-EtOAc混合溶剂或体积比为1:2的石油醚-CH2Cl2混合溶剂。
5.根据权利要求2所述含功能化膦配体的铁铁氢化酶模型物的制备方法,其特征在于:所述步骤3)中丙二酸、4-二甲氨基吡啶(DMAP)、二环己基碳二亚胺(DCC)、CH2Cl2与一级目标化合物的用量比为0.46mmol:0.56mmol:1.06mmol:20mL:0.23-0.46mmol。
6.根据权利要求2所述含功能化膦配体的铁铁氢化酶模型物的制备方法,其特征在于:所述步骤4)中混合溶剂为体积比为2:3的石油醚-CH2Cl2混合溶剂。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610828784.6A CN106632512A (zh) | 2016-09-18 | 2016-09-18 | 一类含功能化膦配体的铁铁氢化酶模型物及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610828784.6A CN106632512A (zh) | 2016-09-18 | 2016-09-18 | 一类含功能化膦配体的铁铁氢化酶模型物及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106632512A true CN106632512A (zh) | 2017-05-10 |
Family
ID=58851788
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610828784.6A Pending CN106632512A (zh) | 2016-09-18 | 2016-09-18 | 一类含功能化膦配体的铁铁氢化酶模型物及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106632512A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109331879A (zh) * | 2018-09-29 | 2019-02-15 | 四川理工学院 | 一种adt类[铁铁]氢化酶模型物及其合成方法 |
-
2016
- 2016-09-18 CN CN201610828784.6A patent/CN106632512A/zh active Pending
Non-Patent Citations (1)
Title |
---|
赵培华: "[铁铁]及[镍铁]-氢化酶活性中心模型物及相关簇合物的设计合成研究", 《南开大学博士学位论文》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109331879A (zh) * | 2018-09-29 | 2019-02-15 | 四川理工学院 | 一种adt类[铁铁]氢化酶模型物及其合成方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108586547B (zh) | 基于亚磷酸酯和不饱和氮杂环卡宾的混配型镍(ii)配合物的制备方法 | |
CN105753700B (zh) | 一种乙炔羰基化合成丙烯酸甲酯的方法 | |
Che et al. | Novel binuclear platinum (III) octaphosphite complexes | |
Ren et al. | Novel vanadium (III) complexes with rigid phenylpolycarboxylate ligands: synthesis, structures and application in C–H bond activation | |
González-Sebastián et al. | Reduction of CO 2 and SO 2 with low valent nickel compounds under mild conditions | |
KR20150037307A (ko) | 신규한 네오디뮴 화합물 및 이를 포함하는 디엔 중합용 촉매 | |
Ochida et al. | Phosphorus Ligands with a Large Cavity: Synthesis of Triethynylphosphines with Bulky End Caps and Application to the Rhodium‐Catalyzed Hydrosilylation of Ketones | |
CN106674288B (zh) | 一种含单膦配体的氧杂丙撑类[铁铁]氢化酶活性中心模型物及其合成方法 | |
CN106632512A (zh) | 一类含功能化膦配体的铁铁氢化酶模型物及其制备方法 | |
CN106478737A (zh) | 含功能化氮杂丙撑桥及氮杂卡宾配体的铁铁氢化酶模型物及其合成方法 | |
Bai et al. | Di-, tri-and tetraphosphine-substituted Fe/Se carbonyls: synthesis, characterization and electrochemical properties | |
CN111763226A (zh) | 碳酸酯的硼氢化反应方法 | |
Sakae et al. | Hydrophosphination of Propargylic Ethers with Diphenylphosphine in the Presence of LiHMDS, N-Heterocyclic Carbene, and Ti (NMe2) 4 | |
CN108129424A (zh) | 一种双齿膦配体聚合物负载钯催化剂催化糠醛类衍生物脱羰反应的方法 | |
Zahirović et al. | Ruthenium organometallics of chloro-substituted 2′-hydroxychalcones–A story of catecholase biomimetics beyond copper | |
CN102942548A (zh) | 一种δ-十二内酯的合成方法 | |
Baldovino-Pantaleón et al. | Reactivity of C6F5S-P (C6H5) 2 with [M3 (CO) 12](M= Fe, Ru, Os). The X-ray crystal structures of [Fe2 (μ-SC6F5)(μ-PPh2)(CO) 6],[Ru4 (μ3-SPPh2) 2 (μ-SC6F5) 2 (μ-PPh2) 2 (SC6F5) 2 (CO) 6] and [Os3 (η1-Ph2P-SC6F5)(CO) 11] | |
Pearson | Protonation of tricarbonyldieneiron complexes: Acid-catalysed cyclization of tricarbonylmyrceneiron | |
Ngumbu et al. | Transformation of bio‐derived levulinic acid to gamma‐valerolactone by cyclopentadienone ruthenium (0) catalyst precursors bearing simple supporting ligands | |
Cook et al. | A multimetal-ligand cooperative approach to CO2 activation | |
JP6538580B2 (ja) | 水素酸化触媒 | |
CN105218595B (zh) | 一种含[2P2N]Cu(I)光敏剂的铁铁氢化酶模型物及其制备方法 | |
CN102838633B (zh) | 一种制备γ-氧代膦酸酯的方法 | |
CN106565794A (zh) | 含质子性氮‑磷单齿配体的铁羰基化合物及其制备方法 | |
Kim et al. | Mechanistic study of half-titanocene-based reductive pinacol coupling reaction |
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 |
Application publication date: 20170510 |
|
WD01 | Invention patent application deemed withdrawn after publication |