CN109651446B - Monophosphine-substituted bridged azapropane bridged iron-iron hydrogenase model compound and synthesis method and application thereof - Google Patents
Monophosphine-substituted bridged azapropane bridged iron-iron hydrogenase model compound and synthesis method and application thereof Download PDFInfo
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- 108010020056 Hydrogenase Proteins 0.000 title claims abstract description 19
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- NJFMNPFATSYWHB-UHFFFAOYSA-N ac1l9hgr Chemical compound [Fe].[Fe] NJFMNPFATSYWHB-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 150000001875 compounds Chemical class 0.000 title abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- UNUDYSFTRMTXBJ-UHFFFAOYSA-N CO.C1(=CC=CC=C1)PC1=CC=CC=C1 Chemical compound CO.C1(=CC=CC=C1)PC1=CC=CC=C1 UNUDYSFTRMTXBJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 4
- 239000012265 solid product Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims abstract 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 230000006324 decarbonylation Effects 0.000 claims description 3
- 238000006606 decarbonylation reaction Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 108010072136 iron hydrogenase Proteins 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005057 refrigeration Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- QPECWWIZMZHSDR-UHFFFAOYSA-N diphenylphosphanylmethanol Chemical compound C=1C=CC=CC=1P(CO)C1=CC=CC=C1 QPECWWIZMZHSDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003446 ligand Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000001294 propane Substances 0.000 abstract description 2
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 5
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- -1 diphenylphosphine hydrogen Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 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
- C07F15/02—Iron compounds
- C07F15/025—Iron 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
- B01J31/003—Catalysts comprising hydrides, coordination complexes or organic compounds containing enzymes
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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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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Abstract
The invention discloses a monophosphine-substituted bridged aza-propane bridged ferroiron hydrogenase model compound and a synthesis method and application thereof, wherein the chemical formula of the model compound is Fe2[(μ‑SCH2)2NCH2PPh2](CO)5The structural formula is as follows:. During synthesis, under the protection of nitrogen, adding diphenylphosphine into a round-bottom flask, dropwise adding a mixed solution of deoxygenated formaldehyde water solution and concentrated hydrochloric acid at 0 ℃, and stirring for reaction to obtain quaternary phosphonium salt; then taking the quaternary phosphonium salt, the deoxygenated methanol and the triethylamine to react at room temperature to obtain diphenylphosphine methanol; will (a) toμ‑SCH2NHCH2S‑μ)Fe2(CO)6Dissolving in deoxygenated dichloromethane, and adding Me3NO·2H2O, stirring and reacting at room temperature; and adding the obtained diphenylphosphine methanol into the reaction solution, and magnetically stirring at room temperature to obtain a dark red solid product. The invention belongs to the technical field of metal organic synthesis, has simple synthesis method, easy operation, mild condition and normal-temperature reaction, and is suitable for synthesizing most of iron-iron hydrogenase of monophosphine ligand.
Description
Technical Field
The invention belongs to the technical field of metal organic chemistry and hydrogenase model synthesis, and particularly relates to a monophosphine-substituted bridged azapropane bridged ferric iron hydrogenase model and a synthesis method and application thereof.
Background
The search for new, clean and harmless renewable energy sources is urgent need for realizing sustainable development of human society. The hydrogen has the characteristics of no toxicity, high combustion efficiency, no pollution of combustion products, cyclic utilization and the like, is generally accepted as an ideal energy source for the future of human beings, resources and pollution are the most serious problems in the world at present, and the hydrogen is taken as a clean energy source and has significant significance for human environmental protection. Therefore, chemists have conducted chemical simulation and biomimetic research on hydrogenases by using the [2Fe2S ] skeleton as an active center. Most of iron-iron hydrogenase models reported in the prior literature are only monosubstituted and connected phosphine-containing ligand hydrogenase models or are modified on bridgehead atoms, and the invention synthesizes a novel phosphine hydrogenase active center [2Fe-2S ] model which bridges an aza-propane bridge and has a rigid structure.
Disclosure of Invention
The invention aims to provide a monophosphine-substituted bridged azapropane bridged ferroiron hydrogenase model, a synthesis method and application thereof, wherein the model has a stable rigid structure containing monophosphine ligands. The synthetic method of the model substance is simple, the reaction condition is mild, the operation is easy, and the model substance can be prepared in large scale.
The technical scheme for realizing the aim of the invention is as follows:
a monophosphine-substituted bridged azapropane bridged ferroiron hydrogenase model compound with a chemical formula of Fe2[(μ-SCH2)2NCH2PPh2](CO)5The structural formula is as follows:
the invention also provides a synthesis method of the monophosphine-substituted bridged azapropane bridged ferroiron hydrogenase model compound, and the synthesis route is as follows:
the specific synthesis method comprises the following steps:
1) under the protection of nitrogen, adding diphenylphosphine into a round-bottom flask, dropwise adding a mixed solution of a formaldehyde aqueous solution and concentrated hydrochloric acid at 0 ℃, carrying out magnetic stirring reaction, changing the reaction solution from turbid to clear, placing the reaction solution in a refrigerator for refrigeration, precipitating white crystals, and carrying out suction filtration to obtain quaternary phosphonium salt [ Ph ]2P(CH2OH)2]+Cl–;
2) Under the protection of nitrogen, in another round-bottom flask, quaternary phosphonium salt [ Ph ] is added2P(CH2OH)2]+Cl–And the methanol is magnetically stirred and completely dissolved, and then triethylamine is added for reaction at room temperature to obtain diphenylphosphine methanol;
3) under the protection of nitrogen, (mu-SCH) was added2NHCH2S-μ)Fe2(CO)6Dissolving in dichloromethane, and adding dropwise decarbonylation agent Me in methanol3NO·2H2O, stirring and reacting at room temperature, wherein the reaction solution changes from orange red to brownish red;
4) adding the obtained diphenylphosphine methanol into the reaction liquid obtained in the step 3) under the protection of nitrogen, magnetically stirring at room temperature, changing the reaction liquid into dark red, tracing by a TLC point plate, adding silica gel powder when the raw material point disappears, spin-drying the solvent, separating the crude product by silica gel column chromatography, and eluting to obtain a dark red solid product, namely the monophosphine-substituted bridged azapropane bridged ferroiron hydrogenase model.
The synthesis method comprises the following steps:
the mass ratio of the diphenylphosphine hydrogen, the formaldehyde aqueous solution and the concentrated hydrochloric acid in the step 1) is 1:2: 1.
Step 2) the quaternary phosphonium salt [ Ph2P(CH2OH)2]+Cl–The ratio of the amount of methanol to the amount of triethylamine was 1.8mmol, 20mL, 1.8 mmol.
Step 3) the (. mu. -SCH)2NHCH2S-μ)Fe2(CO)6The dosage ratio of the dichloromethane to the dichloromethane is 1mmol:30 mL;
methanol and Me3NO·2H2The dosage ratio of O is 10mL to 1 mmol;
(μ-SCH2NHCH2S-μ)Fe2(CO)6and Me3NO·2H2The mass ratio of O is 1: 1.
Step 4) said diphenylphosphinomethanol and [ (mu-SCH)2NHCH2S-μ)Fe2(CO)6]The mass ratio of (a) to (b) is 1: 1; separating by silica gel column chromatography, wherein the eluent is petroleum ether and dichloromethane is 4: 1.
The invention further provides application of the monophosphine-substituted bridged azapropane bridged ferric iron hydrogenase model in electrocatalysis of protonic acid reduction to hydrogen.
The invention has the beneficial effects that:
1. the invention synthesizes a novel hydrogenase active center [2Fe-2S ] model substance which has a rigid structure and contains monophosphine, and is characterized by infrared, nuclear magnetism and crystal structure. Compared with other similar models, the rigid structure can improve the stability of the models.
2. The synthesis method is simple, easy to operate, mild in condition and suitable for synthesis of most of iron-iron hydrogenase of the monophosphine ligand, and the reaction is carried out at normal temperature.
3. The model object of the invention is a stable rigid structure containing monophosphine ligand, thereby improving the electrocatalytic activity and hydrogen production capability of the model object. In electrochemical experiments. After the protonic acid is added, the current density is increased, and the catalyst has a good function of catalyzing hydrogen production and is an electrocatalyst with potential practical application value.
Drawings
FIG. 1 is a crystal structure diagram of a model of an embodiment;
FIG. 2 is an infrared image of a model object according to an embodiment;
FIG. 3 is a NMR hydrogen spectrum of a model of an example;
FIG. 4 is a NMR spectra of phosphorus in the form of an example;
FIG. 5 is a cyclic voltammogram of a model object of an example.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited thereto.
Example (b):
a monophosphine-substituted bridged azapropane bridged ferroiron hydrogenase model of the formula:
Fe2[(μ-SCH2)2NCH2PPh2](CO)5the synthesis method of the model substance comprises the following steps:
1) under the protection of nitrogen, 0.27mol of diphenylphosphine is added into a 250mL round-bottom flask, 0.54mol of 40% formaldehyde aqueous solution and 0.27mol of 36% concentrated hydrochloric acid are dropwise added at 0 ℃, the mixture is magnetically stirred for reaction for 10 hours, the reaction solution is changed from turbid to clear, the reaction solution is placed into a refrigerator for refrigeration, white crystals are separated out, and the filtration is carried out to obtain quaternary phosphonium salt [ Ph ]2P(CH2OH)2]+Cl–68g, yield 90%;
2) under the protection of nitrogen, 1.8mmol of quaternary phosphonium salt [ Ph ] is added into a 50mL round-bottom flask2P(CH2OH)2]+Cl–Adding 20mL of methanol, magnetically stirring to completely dissolve, adding 1.8mmol of triethylamine, and reacting at room temperature to obtain diphenylphosphine methanol;
3) under nitrogen protection, 1mmol of [ (mu-SCH) ] is added into a 100mL Schlenk flask2NHCH2S-μ)Fe2(CO)6]And 30mL of methylene chloride, and after dissolution, 1mmol of the decarbonylation reagent Me dissolved in 10mL of methanol was added dropwise3NO·2H2O, stirring for 20min at room temperature, and changing the reaction liquid from orange to brownish red;
4) under the protection of nitrogen, injecting 1mmol of the obtained diphenylphosphine methanol into the reaction solution obtained in the step 3), magnetically stirring at room temperature, changing the reaction solution into dark red, tracing by a TLC point plate, removing a raw material point after 4 hours, changing the reaction solution into dark red, adding a small amount of silica gel powder, spin-drying a solvent, separating a crude product by silica gel column chromatography, and eluting by petroleum ether/dichloromethane (4/1, v/v) to obtain 0.272g of a dark red solid product with the yield of 48%.
Through detection: product Fe2[(μ-SCH2)2NCH2PPh2](CO)5Melting point: 105.8 to 107.3 ℃. Dissolving the solid in petroleum ether, dichloromethane, ethyl acetate, acetonitrile, ethanol, methanol, etc.; is slightly soluble in n-hexane and n-pentane; 0.2g of the model was taken and made into a saturated solution with methylene chloride and n-hexane (4/1, v/v), and the saturated solution was refrigerated in a refrigerator to obtain crystals of the model as shown in FIG. 1.
The model was characterized by infrared, nuclear magnetic, as shown in FIGS. 2-4.
The structural data of the model are characterized as follows:
IR(KBr disk):VCO:2044.45cm–1,1969.19cm–1,1926.69cm–1;
1H NMR(500MHz,CD2Cl2)δ:7.94–7.62(m,PPhH,4H),7.53(d,PPhH,6H),3.85(d,J=13.1Hz,NCH2S,2H),3.73(d,NCH2S,1H),3.37(s,NCH2P,2H);
31P NMR(202MHz,CD2Cl2)δ:39.50,39.34(d,PPh2)。
electrochemical experiments are carried out on the model substance of the monophosphine-substituted bridged azapropane bridged iron-iron hydrogenase in the embodiment, and the model substance is proved to have the function of catalyzing hydrogen production and can be applied to catalyzing protonic acid to reduce hydrogen.
The test was carried out on CHI60 electrochemical workstation, using a three-electrode system, the working electrode being a glassy carbon electrode (diameter 3mm) and the reference electrode being non-aqueous Ag/AgTen pieces of clothElectrode (0.01mol/L AgNO)3CH (A) of3CN solution), the auxiliary electrode is a platinum wire. The solvent used in the test was chromatographically pure acetonitrile, and the supporting electrolyte was n-Bu4NPF6. The acid used in the experiment was trifluoromethanesulfonic acid, which was used by pipetting with a pipette. The test method comprises the following steps: before use, the reference electrode, the auxiliary electrode and the glassy carbon electrode are subjected to ultrasonic treatment for 30min by using dichloromethane and washed by using acetonitrile; wetting a polishing plate with the thickness of 3 mu m with deionized water, polishing the glassy carbon electrode in a shape of 8 for 10min, grinding until the surface of the glassy carbon electrode is smooth, washing with the deionized water, performing ultrasonic treatment with acetonitrile for 10min, and wiping with a piece of lens wiping paper. The reference electrode and the auxiliary electrode are both washed with acetonitrile for use. Before the test, nitrogen is introduced into the solution to remove oxygen for 20min so as to remove oxygen in the solution, and the test is carried out under the protection of nitrogen. Absorbing (0eq-9eq) trifluoromethanesulfonic acid by using a pipette respectively, and testing cyclic voltammograms at different concentrations respectively, wherein all potentials are ferrocene (Fc/Fc)+) And (6) correcting.
The model shows the catalytic performance, as shown in FIG. 5, of the model in n-Bu containing 1mmol of the model4NPF6PerCN solution A cyclic voltammogram of trifluoromethanesulfonic acid (0eq,1eq,3eq,5eq,7eq,9eq) was added at a sweep rate of 100 mv/s. As can be seen from fig. 5: in an electrochemical test system containing 1mmol of model substance, the current of a reduction peak is continuously increased along with the increase of the concentration of protonic acid, the potential change of the corresponding peak is small, and the model substance is proved to have the characteristic of catalyzing hydrogen production.
Claims (2)
1. A method for synthesizing a monophosphine-substituted bridged azapropane-bridged ferroiron hydrogenase model is characterized in that the synthetic route is as follows:
the synthesis method comprises the following steps:
1) under the protection of nitrogen, adding diphenylphosphine into a round-bottom flask, dropwise adding a mixed solution of a formaldehyde aqueous solution and concentrated hydrochloric acid at 0 ℃, carrying out magnetic stirring reaction, changing the reaction solution from turbid to clear, placing the reaction solution in a refrigerator for refrigeration, precipitating white crystals, and carrying out suction filtration to obtain quaternary phosphonium salt [ Ph ]2P(CH2OH)2]+Cl–;
The mass ratio of the diphenylphosphine to the formaldehyde aqueous solution to the concentrated hydrochloric acid is 1:2: 1;
2) under the protection of nitrogen, in another round-bottom flask, quaternary phosphonium salt [ Ph ] is added2P(CH2OH)2]+Cl–And the methanol is magnetically stirred and completely dissolved, and then triethylamine is added for reaction at room temperature to obtain diphenylphosphine methanol;
the quaternary phosphonium salt [ Ph2P(CH2OH)2]+Cl–The dosage ratio of the methanol to the triethylamine is 1.8mmol to 20mL to 1.8 mmol;
3) under the protection of nitrogen gas, the mixture is preparedμ-SCH2NHCH2S-μ)Fe2(CO)6Dissolving in dichloromethane, and adding dropwise decarbonylation agent Me dissolved in methanol3NO·2H2O, stirring and reacting at room temperature, wherein the reaction solution changes from orange red to brownish red;
the above (A) toμ-SCH2NHCH2S-μ)Fe2(CO)6The dosage ratio of the dichloromethane to the dichloromethane is 1mmol:30 mL;
methanol and Me3NO·2H2The dosage ratio of O is 10mL to 1 mmol;
(μ-SCH2NHCH2S-μ)Fe2(CO)6and Me3NO·2H2The mass ratio of O is 1: 1;
4) adding the obtained diphenylphosphine methanol into the reaction liquid obtained in the step 3) under the protection of nitrogen, magnetically stirring at room temperature, changing the reaction liquid into dark red, tracing by a TLC point plate, adding silica gel powder when a raw material point disappears, spin-drying a solvent, separating a crude product by silica gel column chromatography, and eluting to obtain a dark red solid product, namely a monophosphine-substituted bridged azapropane bridged iron-iron hydrogenase model;
said diphenylphosphinomethanol and (A)μ-SCH2NHCH2S-μ)Fe2(CO)6The mass ratio of (a) to (b) is 1: 1;
and (3) performing silica gel column chromatography separation, wherein an eluent is petroleum ether and dichloromethane, and the volume ratio of the petroleum ether to the dichloromethane =4: 1.
2. Use of a monophosphine-substituted bridged azapropane bridged ferric iron hydrogenase model prepared according to claim 1 to electrocatalyze the reduction of protonic acid to hydrogen.
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Jiao He等.A New Route to the Synthesis of Phosphine-Substituted Diiron Aza and Oxadithiolate Complexes.《Organometallics》.2017,第36卷第1322-1330页,特别是Scheme 2,第1322页左栏第1段,第1323页左栏第1段. * |
Redox Reactions of [FeFe]-Hydrogenase Models Containing an Internal Amine and a Pendant Phosphine;Dehua Zheng等;《Inorg. Chem.》;20140114;第53卷;第1555-1561页 * |
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