CN104370975A - Butterfly-shaped (Fe2SP) hydrogenase model material and preparation method thereof - Google Patents

Butterfly-shaped (Fe2SP) hydrogenase model material and preparation method thereof Download PDF

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CN104370975A
CN104370975A CN201410740617.7A CN201410740617A CN104370975A CN 104370975 A CN104370975 A CN 104370975A CN 201410740617 A CN201410740617 A CN 201410740617A CN 104370975 A CN104370975 A CN 104370975A
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triethylamine
butterfly
shaped
hydrogenase
iron
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CN104370975B (en
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宋礼成
张伟伟
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Nankai University
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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 System
    • C07F15/02—Iron compounds

Abstract

The invention provides a butterfly-shaped (Fe2SP) hydrogenase model material which belongs to a sort of (FeFe)-hydrogenase model material with the skeleton of Fe2 (mu-S)(mu-PR) through mu-CO intermediate intramolecular synthesis. The bridging atoms of the model material are atoms S and atoms P; the material can be presented through the chemical structural formula that (img file = 'DDA0000626951390000011.TIF' wi = '488' he = '310' /); n presents the number of carbon atoms as 0 or 1; R presents chlorine, phenyl, methoxyl, oxethyl, diethylamino or 4-bromobutoxy. The method has the advantages that the preparation method of the butterfly-shaped (Fe2SP) hydrogenase model material is simple in process, raw materials are low in cost and easy to obtain, the reaction condition is mild, various (Fe2SP) hydrogenase model material can be prepared, and the application range in the field of the Fe Fe hydrogenase biomimetic chemistry can be expanded accordingly.

Description

A kind of butterfly-shaped two iron sulphur phosphorus hydrogenase model things and preparation method thereof
Technical field
The invention belongs to metal organic and energy science field, particularly a kind of butterfly-shaped two iron sulphur phosphorus hydrogenase model things and preparation method thereof.
Background technology
Iron iron hydrogenase to be a kind ofly present in multiple-microorganism body and to have the metalloenzyme that efficient catalytic proton reduction generates hydrogen ability, the research interest that people are dense has just been caused since being found, people " artificial enzyme " attempted by the research of iron iron hydrogenase biomimetic chemistry being a kind of Cheap highly effective of synthesis carrys out catalysis and produces hydrogen, to alleviate significant problem (Ogino, the H. such as day by day serious energy shortage and environmental pollution; Inomata, S.; Tobita, H.Chem.Rev.1998,98,2093-2122; Fontecilla-Camps, J.C.; Volbeda, A.; Cavazza, C.; Nicolet, Y.Chem.Rev.2007,107,4273-4303; Darensbourg, M.Y.; Lyon, E.J.; Smee, J.J.Coord.Chem.Rev.2000,206-207,533-561).Up to now, the iron iron hydrogenase model thing of bibliographical information is mostly containing [Fe 2s 2] butterfly-shaped skeleton, but containing [Fe 2sP] research of framework compound is but relatively little, and the overwhelming majority is all open chain type compound, structurally to differ greatly (Evans, D.J. with iron iron hydrogenase activity center; Pickett, C.J.Chem.Soc.Rev., 2003,32,268-275; Simmons T.R.; Berggren, G.; Bacchi, M.; Fontecave, M.; Artero, V.Coord.Chem.Rev.2014,270-271,127-150).
Butterfly-shaped iron sulphur μ-CO intermediate has very high reactive behavior, can with multiple organic and inorganic and metal organic substrates generation nucleophilic reaction, and itself skeleton and iron iron hydrogenase activity center similar, therefore it is expected to have significant application value (Seyferth, D. in their research in iron iron hydrogenase bionic catalysis; Womack, G.B.; Dewan, J.C.Organometallics, 1985,4,398-400; Song Licheng, the Advances In Chemistry of novel butterfly-shaped Fe/E/ μ-CO (E=S, Se, Te) bunch salt, Chinese science B collects chemistry, 2008,38,10,851-866; Song, L.-C.Trends.Organomet.Chem.1999,3,1-20).We utilize butterfly-shaped iron sulphur μ-CO intermediate directly to react with phosphorus trihalide and phenylphosphonic dichloride electrophilic reagent, are generating [Fe 2sP] continue to add alkali after open chain type compound and impel its intramolecular condensation to close ring, generate the Novel iron iron hydrogenase model thing more similar to virgin iron iron hydrogenase activity center.
Summary of the invention
The object of the invention is for above-mentioned technical Analysis, a kind of butterfly-shaped two iron sulphur phosphorus hydrogenase model things and preparation method thereof are provided, these butterfly-shaped two iron sulphur phosphorus hydrogenase model things adopt intramolecular condensation close the method for ring or be prepared the method that P-X (X=Cl, Br) functional group modifies, technique is simple, cheaper starting materials is easy to get, reaction conditions is gentle, can prepare multiple [Fe 2sP] type hydrogenation enzyme model thing to be to expand application in iron iron hydrogenase biomimetic chemistry field.
Technical scheme of the present invention:
A kind of butterfly-shaped two iron sulphur phosphorus hydrogenase model things, it uses a class of μ-CO intermediate molecule internal condensation synthesis with Fe 2[FeFe]-hydrogenase model thing that (μ-S) (μ-PR) is skeleton, this class model thing bridge formation atom is respectively S atom and P atom, and it has chemical structural formula as follows:
In structural formula: n represents that the number of carbon atom is herein 0 or 1; R is chlorine, phenyl, methoxyl group, oxyethyl group, diethylamino or 4-bromine butoxy.
A preparation method for described butterfly-shaped two iron sulphur phosphorus hydrogenase model things, step is as follows:
1) be equipped with at nitrogen replacement in the reaction flask stirring magneton, tri-iron dodecacarbonyl added in organic solvent and to mix, obtaining mixed solution;
2) in above-mentioned mixed solution, add hydroxy thiol and triethylamine, reaction 15min, obtains reaction solution;
3) after adding electrophilic reagent in above-mentioned reaction solution continue reaction 6h, then add triethylamine stir spend the night or the 4h that reflux, obtain redness suspension liquid;
4) reaction 6h is continued continue to add triethylamine or triethylamine and methyl alcohol or triethylamine and diethylamine in above-mentioned suspension liquid after;
5) decompressing and extracting solvent, uses dichloromethane extraction resistates, is that the dichloromethane-petroleum ether of 1:7 carries out TLC separation as developping agent, collects red mass-tone band by volume ratio, obtains red solid and is containing [Fe 2sP] compound of skeleton.
Described step 1) in organic solvent be tetrahydrofuran (THF) or ether; The amount ratio of tri-iron dodecacarbonyl and organic solvent is 3mmol:30mL.
Described step 2) in hydroxy thiol be o-hydroxy thiophenol or adjacent mercapto benzyl alcohol; The amount ratio of mixed solution, hydroxy thiol and triethylamine is 30mL:3mmol:3mmol.
Described step 3) in electrophilic reagent be phosphorus trichloride, phenyl dichloro phosphorus or phosphorus tribromide; The amount ratio of reaction solution, electrophilic reagent, triethylamine is 30mL:4.5mmol:3mmol.
Described step 4) in the amount ratio of suspension liquid and triethylamine be 30mL:3mmol; The amount ratio of suspension liquid, triethylamine, methyl alcohol is 30mL:3mmol:5mmol; The amount ratio of suspension liquid, triethylamine, diethylamine is 30mL:3mmol:5mmol.
Functional modification of the present invention under triethylamine condition, adds methyl alcohol or diethylamine is obtained by reacting.When using phosphorus tribromide in the present invention as electrophilic reagent, be surprised to find that solvents tetrahydrofurane, ether can participate in reaction by C-O bond rupture, obtain novel functional modification product.
The beneficial effect of present method is: this butterfly-shaped [Fe 2sP] preparation method's technique of type hydrogenation enzyme model thing is simple, and cheaper starting materials is easy to get, and reaction conditions is gentle, can prepare multiple [Fe 2sP] type hydrogenation enzyme model thing to be to expand application in iron iron hydrogenase biomimetic chemistry field.
Embodiment
For understanding the present invention better, the solution of the present invention will be further illustrated by specific embodiment below, but protection scope of the present invention should comprise the full content of claim, is not limited thereto.
Embodiment 1:
A preparation method for described butterfly-shaped two iron sulphur phosphorus hydrogenase model things, the chemical formula of described model thing is [μ-SC 6h 4oP (Ph)-μ] Fe 2(CO) 6, preparation process is as follows:
Concrete preparation process is as follows:
1), under nitrogen protection, being equipped with in the 100mL round bottom Schlenk flask stirring magneton, adding 1.5g tri-iron dodecacarbonyl (3.0mmol) and 30mL tetrahydrofuran (THF), obtaining mixed solution;
2) in above-mentioned mixed solution, add 0.3mL o-hydroxy thiophenol (3.0mmol) and 0.42mL triethylamine (3.0mmol) under stirring, solution is in green, and stirring at room temperature 15min, obtains reaction solution;
3) in above-mentioned reaction solution, add 0.60mL phenylphosphonic dichloride (4.5mmol) continue afterwards to react 6h, then add 0.42mL triethylamine (3.0mmol) back flow reaction 4h;
4) in above-mentioned suspension liquid, continue to add 0.42mL triethylamine (3.0mmol) to continue afterwards to react 6h;
5) decompressing and extracting solvent, uses dichloromethane extraction resistates, is that the dichloromethane-petroleum ether of 1:7 carries out TLC separation as developping agent, collects red mass-tone band by volume ratio, obtains red solid 166mg and is containing [Fe 2sP] framework compound, productive rate 10.8%.
Product structure data characterization is as follows: fusing point: 125-126 DEG C; Anal.Calcd for C 18h 9fe 2o 7pS:C, 42.23; H, 1.77.Found:C, 42.15; H, 1.56.IR (KBr disk): ν c ≡ O2069 (s), 2029 (vs), 1979 (vs) cm -1. 1h NMR (400MHz, CDCl 3): 8.07-8.01 (m, 2H), 7.80-7.79 (m, 1H), 7.68-7.61 (m, 3H), 7.33-7.26 (m, 1H), 7.05-6.95 (m, 2H) ppm. 31p NMR (161.9MHz, CDCl 3): 260.73 (s) ppm. 13c NMR (100MHz, CDCl 3): 209.26 (s), 154.02 (s), 137.09 (s), 133.86 (s), 132.30 (s), 132.00 (s), 130.50 (s), 129.03 (s), 122.69 (s), 120.41 (s), 115.31 (s), 115.07 (s) ppm.
Embodiment 2:
A preparation method for described butterfly-shaped two iron sulphur phosphorus hydrogenase model things, the chemical formula of described model thing is [μ-SC 6h 4oP (Cl)-μ] Fe 2(CO) 6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 1, difference is: step 3) in after stirring at room temperature 15min, change into and add 0.39mL phosphorus trichloride (4.5mmol), after adding 0.42mL triethylamine again, change stirred overnight at room temperature aftertreatment reaction into, obtain red solid 182mg containing [Fe 2sP] framework compound, productive rate 12.9%.
Product structure data characterization is as follows: fusing point: 106-107 DEG C; Anal.Calcd for C 12h 4clFe 2o 7pS:C, 30.64; H, 0.86.Found:C, 30.85; H, 1.02.IR (KBr disk): ν c ≡ O2077 (vs), 2040 (vs), 1995 (vs) cm -1. 1h NMR (400MHz, CDCl 3): 7.74 (d, J=7.7Hz, 1H), 7.40-7.26 (m, 1H), 7.09-7.03 (m, 2H) ppm. 31p NMR (161.9MHz, CDCl 3): 299.25 (s) ppm. 13c NMR (100MHz, CDCl 3): 208.50 (s), 208.16 (s), 155.02 (s), 133.84 (s), 131.07 (s), 123.50 (s), 120.43 (s), 114.47 (s), 114.21 (s) ppm.
Embodiment 3:
A preparation method for described butterfly-shaped two iron sulphur phosphorus hydrogenase model things, the chemical formula of described model thing is [μ-SC 6h 4oP (OMe)-μ] Fe 2(CO) 6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 2, difference is: step 4) in add triethylamine after change into and add 0.42mL triethylamine (3.0mmol) and 0.2mL methyl alcohol (5.0mmol) reacts 6h, obtain red solid 147mg and be containing [Fe 2sP] framework compound, productive rate 10.5%.
Product structure data characterization is as follows: fusing point: 118-119 DEG C; Anal.Calcd for C 13h 7fe 2o 8pS:C, 33.51; H, 1.51.Found:C, 33.37; H, 1.48.IR (KBr disk): ν c ≡ O2076 (s), 2031 (vs), 1989 (vs), 1962 (vs) cm -1. 1h NMR (400MHz, CDCl 3): 7.74-7.72 (m, 1H), 7.34-7.26 (m, 1H), 7.01-6.95 (m, 2H), 5.30 (s, 3H) .ppm. 31p NMR (161.9MHz, CDCl 3): 222.18 (s) ppm. 13c NMR (100MHz, CDCl 3): 209.42 (s), 208.48 (s), 152.79 (s), 134.23 (s), 130.76 (s), 122.95 (s), 120.39 (s), 120.35 (s), 115.65 (s), 69.97 (s), 69.83 (s) ppm.
Embodiment 4:
A preparation method for described butterfly-shaped two iron sulphur phosphorus hydrogenase model things, the chemical formula of described model thing is [μ-SC 6h 4oP (NEt 2)-μ] Fe 2(CO) 6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 3, and difference is: step 4) in change 0.42mL triethylamine (3.0mmol) into and 0.25mL diethylamine (5.0mmol) reacts 6h, obtain red solid 118mg, productive rate 7.7%.
Product structure data characterization is as follows: fusing point: 113-114 DEG C; Anal.Calcd for C 16h 17fe 2nO 7pS:C, 37.90; H, 2.78; N, 2.76.Found:C, 37.62; H, 2.56; N, 3.01.IR (KBr disk): ν c ≡ O2069 (s), 2027 (vs), 1979 (vs) cm -1. 1h NMR (400MHz, CDCl 3): 7.78 (d, J=7.7Hz, 1H), 7.33-7.31 (m, 1H), 7.00-6.93 (m, 2H), 3.67-3.59 (m, 4H), 1.37 (t, J=7.1Hz, 6H) ppm. 31p NMR (161.9MHz, CDCl 3): 265.08 (s) ppm. 13c NMR (100MHz, CDCl 3): 209.37 (s), 154.64 (s), 133.47 (s), 129.89 (s), 122.04 (s), 119.72 (s), 114.59 (s), 114.37 (s), 46.06 (s), 46.04 (s), 13.42 (s) ppm.
Embodiment 5:
A preparation method for described butterfly-shaped two iron sulphur phosphorus hydrogenase model things, the chemical formula of described model thing is [μ-SC 6h 4oP (OCH 2cH 2cH 2cH 2br)-μ] Fe 2(CO) 6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 2, and difference is: 0.43ml phosphorus tribromide (4.5mmol) is replaced 0.39mL phosphorus trichloride (4.5mmol), obtains red solid 237mg, productive rate 15.6%.
Product structure data characterization is as follows: fusing point: 136-137 DEG C; Anal.Calcd for C 16h 12fe 2o 8pS:C, 32.74; H, 2.06.Found:C, 32.52; H, 2.17.IR (KBr disk): ν c ≡ O2072 (s), 2030 (vs), 1983 (vs) cm -1. 1h NMR (400MHz, CDCl 3): 7.76 (d, J=7.8Hz, 1H), 7.37-7.33 (m, 1H), 7.04-7.00 (m, 2H), 4.49-4.45 (m, 2H), 3.54 (t, J=6.2Hz, 2H), 2.39-1.85 (m, 4H) .ppm. 31p NMR (161.9MHz, CDCl 3): 287.80 (s) ppm. 13c NMR (100MHz, CDCl 3): 208.89 (s), 208.84 (s), 153.61 (s), 133.51 (s), 130.27 (s), 122.88 (s), 119.65 (s), 115.60 (s), 115.36 (s), 71.96 (s), 71.83 (s), 33.06 (s), 29.19 (s), 28.81 (s) ppm.
Embodiment 6:
A preparation method for described butterfly-shaped two iron sulphur phosphorus hydrogenase model things, the chemical formula of described model thing is [μ-SC 6h 4oP (OCH 2cH 3)-μ] Fe 2(CO) 6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 2, and difference is: solvent ether (30mL) is replaced tetrahydrofuran (THF) (30mL), obtains red solid 206mg, productive rate 14.3%.
Product structure data characterization is as follows: fusing point: 129-130 DEG C; Anal.Calcd for C 14h 9fe 2o 8pS:C, 35.04; H, 1.89.Found:C, 35.10; H, 2.00.IR (KBr disk): ν c ≡ O2065 (vs), 2021 (vs), 1998 (vs), 1958 (s) cm -1. 1h NMR (400MHz, CDCl 3): 7.75 (d, J=7.7Hz, 1H), 7.36-7.32 (m, 1H), 7.03-6.99 (m, 2H), 4.55-4.43 (m, 2H), 1.59 (t, J=7.0Hz, 3H) ppm. 31p NMR (161.9MHz, CDCl 3): 286.52 (s) ppm. 13c NMR (100MHz, CDCl 3): 208.95 (s), 153.70 (s), 133.54 (s), 130.23 (s), 122.84 (s), 119.72 (s), 115.70 (s), 115.47 (s), 69.45 (s), 69.33 (s), 16.42 (s) ppm.
Embodiment 7:
A preparation method for described butterfly-shaped two iron sulphur phosphorus hydrogenase model things, the chemical formula of described model thing is [μ-SC 6h 4cH 2oP (Ph)-μ] Fe 2(CO) 6) 6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 1, and difference is: adjacent for 420mg mercapto benzyl alcohol (3.0mmol) is replaced 0.3mL o-hydroxy thiophenol (3.0mmol), obtains red solid 124mg, productive rate 7.8%.
Product structure data characterization is as follows: fusing point: 119-120 DEG C; Anal.Calcd for C 19h 11fe 2o 7pS:C, 43.38; H, 2.11.Found:C, 43.47; H, 2.30.IR (KBr disk): ν c ≡ O2060 (s), 2020 (vs), 1985 (vs) cm -1. 1h NMR (400MHz, CDCl 3): 7.96-7.89 (m, 3H), 7.62 (s, 3H), 7.37 (s, 3H), 5.10 (2s, 2H) ppm. 31p NMR (161.9MHz, CDCl 3): 281.90 (s) ppm. 13c NMR (100MHz, d 6-DMSO): 209.86 (s), 136.73 (s), 135.97 (s), 134.12 (s), 132.89 (s), 132.79 (s), 132.46 (s), 131.12 (s), 129.40 (s), 129.07 (s), 128.97 (s), 126.99 (s), 126.78 (s), 126.62 (s), 26.81 (s) ppm.
Embodiment 8:
A preparation method for described butterfly-shaped two iron sulphur phosphorus hydrogenase model things, the chemical formula of described model thing is [μ-SC 6h 4cH 2oP (Cl)-μ] Fe 2(CO) 6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 2, and difference is: adjacent for 420mg mercapto benzyl alcohol (3.0mmol) is replaced 0.3mL o-hydroxy thiophenol (3.0mmol), obtains red solid 137mg, productive rate 9.4%.
Product structure data characterization is as follows: fusing point: 96-97 DEG C; Anal.Calcd for C 13h 6clFe 2o 7pS:C, 32.24; H, 1.25.Found:C, 32.48; H, 1.29.IR (KBr disk): ν c ≡ O2077 (s), 2042 (vs), 2012 (vs), 1984 (vs) cm -1. 1h NMR (400MHz, d 6-DMSO): 7.92-7.80 (m, 1H), 7.45-7.29 (m, 3H), 5.20 (2d, J=20.3Hz, 2H) ppm. 31p NMR (161.9MHz, CDCl 3): 286.57 (s) ppm. 13c NMR (100MHz, CDCl 3): 209.12 (s), 208.67 (s), 138.34 (s), 136.80 (s), 136.51 (s), 134.90 (s), 130.86 (s), 129.11 (s), 128.82 (s), 70.52 (s), 70.39 (s) .ppm.

Claims (6)

1. butterfly-shaped two iron sulphur phosphorus hydrogenase model things, is characterized in that: it uses a class of μ-CO intermediate molecule internal condensation synthesis with Fe 2[FeFe]-hydrogenase model thing that (μ-S) (μ-PR) is skeleton, this class model thing bridge formation atom is respectively S atom and P atom, and it has chemical structural formula as follows:
In structural formula: n represents that the number of carbon atom is herein 0 or 1; R is chlorine, phenyl, methoxyl group, oxyethyl group, diethylamino or 4-bromine butoxy.
2. a preparation method for butterfly-shaped two iron sulphur phosphorus hydrogenase model things as claimed in claim 1, is characterized in that step is as follows:
1) be equipped with at nitrogen replacement in the reaction flask stirring magneton, tri-iron dodecacarbonyl added in organic solvent and to mix, obtaining mixed solution;
2) in above-mentioned mixed solution, add hydroxy thiol and triethylamine, reaction 15min, obtains reaction solution;
3) after adding electrophilic reagent in above-mentioned reaction solution continue reaction 6h, then add triethylamine stir spend the night or the 4h that reflux, obtain redness suspension liquid;
4) reaction 6h is continued continue to add triethylamine or triethylamine and methyl alcohol or triethylamine and diethylamine in above-mentioned suspension liquid after;
5) decompressing and extracting solvent, uses dichloromethane extraction resistates, is that the dichloromethane-petroleum ether of 1:7 carries out TLC separation as developping agent, collects red mass-tone band by volume ratio, obtains red solid and is containing [Fe 2sP] framework compound.
3. the preparation method of butterfly-shaped two iron sulphur phosphorus hydrogenase model things according to claim 2, is characterized in that: described step 1) in organic solvent be tetrahydrofuran (THF) or ether; The amount ratio of tri-iron dodecacarbonyl and organic solvent is 3mmol:30mL.
4. the preparation method of butterfly-shaped two iron sulphur phosphorus hydrogenase model things according to claim 2, is characterized in that: described step 2) in hydroxy thiol be o-hydroxy thiophenol or adjacent mercapto benzyl alcohol; The amount ratio of mixed solution, hydroxy thiol and triethylamine is 30mL:3mmol:3mmol.
5. the preparation method of butterfly-shaped two iron sulphur phosphorus hydrogenase model things according to claim 2, is characterized in that: described step 3) in electrophilic reagent be phosphorus trichloride, phenyl dichloro phosphorus or phosphorus tribromide; The amount ratio of reaction solution, electrophilic reagent, triethylamine is 30mL:4.5mmol:3mmol.
6. the preparation method of butterfly-shaped two iron sulphur phosphorus hydrogenase model things according to claim 2, is characterized in that: described step 4) in the amount ratio of suspension liquid and triethylamine be 30mL:3mmol; The amount ratio of suspension liquid, triethylamine, methyl alcohol is 30mL:3mmol:5mmol; The amount ratio of suspension liquid, triethylamine, diethylamine is 30mL:3mmol:5mmol.
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CN106554373A (en) * 2016-11-08 2017-04-05 四川理工学院 A kind of azepine trimethylene class [ferrum ferrum] hydrogenase activity center model thing containing Phosphine ligands and its synthetic method
CN106674288A (en) * 2016-12-19 2017-05-17 四川理工学院 Oxa-trimethylene (FeFe) hydrogenase active center model compound containing monophosphine ligand and synthesizing method thereof

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Publication number Priority date Publication date Assignee Title
CN106554373A (en) * 2016-11-08 2017-04-05 四川理工学院 A kind of azepine trimethylene class [ferrum ferrum] hydrogenase activity center model thing containing Phosphine ligands and its synthetic method
CN106554373B (en) * 2016-11-08 2018-11-20 四川理工学院 A kind of azepine trimethylene class [iron iron] hydrogenase activity center model object and its synthetic method containing Phosphine ligands
CN106674288A (en) * 2016-12-19 2017-05-17 四川理工学院 Oxa-trimethylene (FeFe) hydrogenase active center model compound containing monophosphine ligand and synthesizing method thereof
CN106674288B (en) * 2016-12-19 2018-10-16 四川理工学院 A kind of oxa- trimethylene class [iron iron] hydrogenase activity center model object and its synthetic method containing monophosphorus ligand

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