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 PDF

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CN109651446B
CN109651446B CN201910061489.6A CN201910061489A CN109651446B CN 109651446 B CN109651446 B CN 109651446B CN 201910061489 A CN201910061489 A CN 201910061489A CN 109651446 B CN109651446 B CN 109651446B
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倪青玲
桂柳成
谢婷婷
韦神骄
马梦霞
王修建
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Guangxi Normal University
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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:
Figure DEST_PATH_IMAGE001
. 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

Monophosphine-substituted bridged azapropane bridged iron-iron hydrogenase model compound and synthesis method and application thereof
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:
Figure BDA0001954273440000011
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:
Figure BDA0001954273440000021
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:
Figure 352001DEST_PATH_IMAGE001
Figure 269142DEST_PATH_IMAGE002
Figure 986562DEST_PATH_IMAGE003
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.
CN201910061489.6A 2019-01-23 2019-01-23 Monophosphine-substituted bridged azapropane bridged iron-iron hydrogenase model compound and synthesis method and application thereof Expired - Fee Related CN109651446B (en)

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A New Route to the Synthesis of Phosphine-Substituted Diiron Aza and Oxadithiolate Complexes;Jiao He等;《Organometallics》;20171231;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 *
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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