CN109126871A - A kind of formate dehydrogenase catalyst and its application - Google Patents
A kind of formate dehydrogenase catalyst and its application Download PDFInfo
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- CN109126871A CN109126871A CN201710454998.6A CN201710454998A CN109126871A CN 109126871 A CN109126871 A CN 109126871A CN 201710454998 A CN201710454998 A CN 201710454998A CN 109126871 A CN109126871 A CN 109126871A
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Abstract
The present invention is a kind of formate dehydrogenase catalyst；Catalyst includes metal and ligand, and metal is iridium, rhodium, ruthenium, cobalt etc., and ligand is the oximido ether compound that amino replaces；Such catalyst is used for the dehydrogenation reaction of formic acid for the first time, and highest TON is up to 505 × 10 at 70 DEG C4, it is the peak reported at present, highest TON is up to 400 × 10 at 90 DEG C4, it is the peak reported at this temperature.
Description
Technical field
The present invention relates to a kind of catalyst for being used for formate dehydrogenase, the oxime ethers specifically replaced by one kind containing amino
The catalyst of the various metal precursors generation of the bidentate or multidentate ligand and iridium, rhodium, ruthenium and cobalt of imine structure.
Background technique
Formic acid is now subjected to people's extensive concern as a kind of liquid hydrogen storage material.Ideal formic acid, which decomposes, produces hydrogen catalysis
System should have the following conditions: (1) catalyst stabilization, raw material are easy to get, and preparation is simple；(2) reaction is solvent-free or is molten with water
Agent；(3) without any additive；(4) pure formic acid or larger concentration formic acid can be decomposed；(5) high catalytic efficiency；(6) reaction can be with
It is a large amount of to carry out and easy to operate, without operation bidirectionals such as protections.Formic acid is decomposed in the homogeneous system reported at present to produce used in hydrogen
Catalyst is mainly the metal complex of ruthenium, rhodium, iridium, iron and cobalt, these catalyst systems can only meet one of conditions above
Or two kinds.They otherwise need to be added alkali to adjust the acid-base property of reaction system or need the reactant using organic solvent
System, and most reactions require safeguard measure, are de-gassed before needing to react to reaction system.Small-scale a small amount of first
The example of sour dehydrogenation reaction is very much (Chem.Soc.Rev.2016,45,3954-3988), does not introduce herein.TON is greater than
2000000 aqueous phase system or pure formate dehydrogenase report have several following.2015, Himeda, Fujita, Mucherman
Et al. report can obtain 2050000 TON (ACS Catal.2015,5,5496-5504), but react and carried out at 60 DEG C, need
Want 580h that can just react, reaction efficiency is low, is not suitable for the practical application for largely quickly needing hydrogen.They reported later
In addition a kind of catalyst, the complex compound formed by pyridine and imidazoles woods class ligand and iridium (Catal.Sci.Technol., 2016,
6,988-992) the formate dehydrogenase reaction time, is shortened into 363h, but catalytic activity or lower.2016, Kawanami
Study group report formate dehydrogenase and can achieve 5000000 TON (ChemSusChem 2016,9,2749-2753), but
It is the reaction time for but needing 2600h, catalytic activity is lower.Williams and his partner use iridium and N, and P- ligand is formed
The pure formate dehydrogenase (Nat.Commun.2016, DOI:10.1038/ncomms11308) of catalyst, by continuous
Formic acid is added, has obtained 2160000 TON, has needed the sodium formate that amount of formic acid 5% is added as additive in reaction system.Li
Study group report iridium and the generated in-situ catalyst of tetrahydropyrimidine class ligand can be in 80 DEG C of catalysis formate dehydrogenases
(Chem.Eur.J., 2015,21,12592-12595), it is average anti-by being continuously added the TON of formic acid available 2400000
Answer rate up to 17000h-1More than.
From these reports it is found that these homogeneous catalysis systems take in the case where additive can be not added in aqueous phase system
Higher TON is obtained, this illustrates that the stability of catalyst is relatively good under the reaction condition that they report, but reactivity is inclined
It is low, be not suitable for the application of rapid, high volume hydrogen.Formate dehydrogenase is an endothermic reaction, and catalysis work can be greatly improved by increasing temperature
Property, but the study group of only Li reports the catalysis reaction result of a large amount of formate dehydrogenases in aqueous phase system at 80 DEG C, thus it is speculated that reason
It may be that these catalyst systems are unstable at high temperature.We have found under study for action, contain amino substituted oximinoether kind ligand and gold
Belonging to the catalyst that iridium is formed has high activity and high stability to formate dehydrogenase reaction in aqueous phase system, can pass through primary first-order equation
4000000 TON is obtained at 90 DEG C, catalytic efficiency is greatly improved, and the catalyst system can also be to solvent-free
Pure formic acid carry out dehydrogenation reaction, the mixture formed to organic solvent and formic acid is similarly effective.As needed, this kind of catalysis
Agent can also be carried out at 70 DEG C, and the TON of primary first-order equation can reach 5050000.The raw material for synthesizing this kind of catalyst is cheap, synthesis step
It is rapid simple, it is suitble to mass production；This kind of catalyst can also can prepare before the reaction complex compound, reaction behaviour with in-situ preparation
Make simple, be not necessarily to any protection and Dehydroepiandrosterone derivative, stability is good, the application in formate dehydrogenase reaction at home and it is external all not
It appears in the newspapers.
Summary of the invention
The present invention provides formate dehydrogenase catalyst in the presence of a kind of no added object, in the composition of in-situ preparation catalyst
The structure E-G of ligand structure A-D and the complex compound catalyst prepared is as follows:
R is H or C1-18One of alkyl or two kinds or more；
N=0 or 1-4
R1=H or C1-18One of alkyl or Si (CH3)3, Si (C2H5)3, Si (CH2Ph)3One of or two kinds with
On；
R2, R3, R4=H or C1-18One of alkyl or two kinds or more；
X is one of CH or N or two kinds；
L1One in=cyclopentadienyl group (Cp), pentamethylcyclopentadiene base (Cp*), substitution or unsubstituted aromatic rings
Kind or two kinds or more, aromatic rings is one of phenyl, naphthalene etc. or two kinds, and the substituent group number on aromatic rings can be 1-5,
Substituent group can be one of methyl, ethyl, isopropyl or two kinds or more；
L2,L3,L4=Cl, CO, H2O,OH,CH3CN,N3, DMF, one of DMSO or two kinds or more；
One of M=iridium, rhodium, ruthenium and cobalt or two kinds or more；
A is the integer between 1 to 6；
V=0, one of+1 ,+2 ,+3 ,+4 ,+5 ,+6；
Be-For anion, Be-Concretely Cl-、Br-、I-、H-、BArF-、NO3 -、BF4 -、PF6 -、 SO4 2-、CO3 2-、PO4 3With
CF3SO3 -One of, e charge number, specially 1, one in 2,3,4,5,6；
V=a × e.
Catalyst provided by the invention can be ligand and metal precursor is generated in-situ, be also possible to the metal prepared
Complex compound, these two types of catalyst may be used to formate dehydrogenase reaction, have high activity and high stability.It is provided by the invention to urge
Agent is used for the dehydrogenation reaction of formic acid, which can carry out in solvent-free pure formic acid, can also be in the condition for having solvent
Lower progress, reaction temperature can carry out between 20-120 DEG C, catalyst concn can between 0.001-3.0mol/L, formic acid it is dense
Degree can be between 0.001-25 mol/L, which does not need any additive.
Compared with existing formate dehydrogenase catalyst, the invention has the following advantages that
1. ligand structure used in the present invention is simple, it is readily synthesized, raw material is cheap and easily-available, is suitble to a large amount of synthesis.
2. formic acid can be catalytically decomposed in catalyst used in the present invention at 90 DEG C, stability is good, high catalytic efficiency, once
Property decompose formic acid TON reach as high as 4000000, highest TON is up to 5050000 at 70 DEG C.
3. catalyst used in the present invention is simple and convenient in the experimental implementation for decomposing formic acid, does not need safeguard measure and take off
Hydrogen processing, has actual application prospect.
Specific embodiment
In order to further illustrate the present invention, following embodiment is enumerated, but scope of the presently claimed invention is not by this
The limitation of a little embodiments.Meanwhile embodiment has been merely given as realizing the partial condition of this purpose, but is not meant to must satisfy
These conditions just can achieve this purpose.
Embodiment 1
It the use of glyoxime L1 is ligand, FA (1.0M, 10.0mL), 60 DEG C of
Weigh [Cp*IrCl2]2(4.0mg, 5.0 μm of ol) and L1 (1.42mg, 12 μm of ol) are put in a reagent bottle, are added
Pure water 1.0mL is configured to the aqueous solution of situ catalytic agent.Magneton, water is added into a Schlenk reaction tube or bottle
(9.42mL) and formic acid (10mmol, 0.38mL), is sealed, branch pipe connects rubber tube with rubber stopper；Reaction flask is put into 60 DEG C
After stirred in water bath stablizes 10 min, the above-mentioned catalyst solution 0.2mL (1.0 μm of ol) prepared is pipetted with liquid-transfering gun and is rapidly joined
In reaction flask, reaction flask is sealed, the band tubing linked on branch pipe is passed through to the 500mL graduated cylinder for filling water handstand in basin at once
In, timing starts, and collects gas with drainage.The gas flow collected in the unit of account time calculates TON and TOF, V (CO2)=
Arrange volume/2 of water, the amount M (H of the substance of the formic acid of decomposition2)=V (H2)/24, specific data are shown in Table example 1 in 1.
Embodiment 2
With embodiment 1, only replace L1 for reacting with ligand (Z)-N'-hydroxypicolinimidamide L2,
It the results are shown in Table example 2 in 1.
Embodiment 3
With embodiment 1, ligand 1 is only used, 2- dimethyl dimethylglyoxime L3 replaces L1 for reacting, the results are shown in Table example in 1
3。
Embodiment 4
With embodiment 1, ligand 1 is only used, 2- diamino glyoxime L4 replaces L1 for reacting, the results are shown in Table example in 1
4。
Embodiment 5
With embodiment 1, ligand 1 is only used, (isopropylamino) the glyoxime L5 of 2- bis- replaces L1 for reacting, as a result sees
Example 5 in table 1.
Embodiment 6
With embodiment 1, only replaces L1 for reacting with bis- ketoxime L6 of ligand piperazine -2,3-, the results are shown in Table example 6 in 1.
Embodiment 7
With embodiment 1, only replaces L1 for reacting with bis- ketoxime L7 of ligand 5- thyl-piperazin -2,3-, the results are shown in Table 1
Middle example 7.
Embodiment 8
With embodiment 1, only replaces L1 for reacting with bis- ketoxime L8 of ligand octahydro quinoxaline -2,3-, the results are shown in Table in 1
Example 8.
Embodiment 9
It weighs Complex-L7 (2.77mg, 5 μm of ol) to be put in a reagent bottle, 5 mL of pure water is added, is configured to network
The aqueous solution of mixture catalyst.Embodiment 1 is shown in other operations, the results are shown in Table example 9 in 1.
Embodiment 10
With embodiment 9, only replaces Complex-L7 for reacting with Complex-L8, the results are shown in Table example 10 in 1.
Embodiment 11
With embodiment 1, (2Z, 6Z)-N'2, N'6-dihydroxypyridine-2,6-bis is only used
(carboximidamide) L9 replaces L1 for reacting, and the results are shown in Table example 11 in 1.
Embodiment 12
With embodiment 1, only replace L1 for reacting with (Z)-N'-hydroxypicolinimidamide L10, as a result
It is shown in Table example 12 in 1.
Embodiment 13
Weigh [Cp*IrCl2]2(4.0mg, 5.0 μm of ol) and L6 (1.73mg, 12 μm of ol) are put in a reagent bottle, are added
Pure water 10mL is configured to the aqueous solution of situ catalytic agent.Magneton, formic acid is added into a Schlenk reaction tube or bottle
(10.0M, 90mL), is sealed with rubber stopper, and branch pipe connects rubber tube, is put it into the container of dress water；Reaction flask is put into 90
DEG C stirred in water bath stablize 40 min after, with liquid-transfering gun by the above-mentioned catalyst solution 1.0mL (1.0 μm of ol) prepared quickly plus
Enter in reaction flask, seal reaction flask, is at once passed through the band tubing linked on branch pipe in the graduated cylinder for filling water handstand in basin,
Timing starts, and emerges to bubble-free, and reaction terminates, and writes down the reaction time, with formic acid remaining in ion chromatography reaction flask
Amount.It is shown in Table example 13 in 2
Embodiment 14
With embodiment 11, the amount of formic acid being only added is 1.8mol (10.0M), the results are shown in Table example 14 in 2.
Embodiment 15
With embodiment 11, the amount of formic acid being only added is 2.2mol (10.0M), the results are shown in Table example 15 in 2.
Embodiment 16
With embodiment 11, the amount of ligand being only added is 3.16mg, Ir/L6=1/2, the results are shown in Table example 16 in 2.
Embodiment 17
With embodiment 11, the amount of ligand being only added is 6.95mg, Ir/L6=1/4.4, the results are shown in Table example 17 in 2.
Embodiment 18
With embodiment 11, the amount of ligand being only added is 11.06mg, Ir/L6=1/7, the results are shown in Table example 18 in 2.
Embodiment 19
With embodiment 11, the amount of formic acid 3.0mol (12.0M) being only added, Ir/L6=1/4.4 the results are shown in Table example in 2
19。
Embodiment 20
With embodiment 11, the amount of formic acid 4.0mol (10.0M) being only added, Ir/L6=1/6 the results are shown in Table example 20 in 2.
Embodiment 21
With embodiment 11, amount of formic acid 5.05mol (10.0M), the Ir/L6=1/6 being only added react at 70 DEG C, as a result
It is shown in Table example 21 in 2.
Embodiment 22
With embodiment 11, the amount of formic acid 4.0mol (10.0M) being only added, Ir/L8=1/6 the results are shown in Table example 22 in 2.
Embodiment 23
With embodiment 11, amount of formic acid 5.0mol (10.0M), the Ir/L8=1/6 being only added react at 70 DEG C, as a result see
Example 23 in table 2.
Embodiment 24
With embodiment 11, the amount of formic acid 1.5mol (15.0M) being only added, Ir/L6=1/6 the results are shown in Table example 24 in 2.
Embodiment 25
With embodiment 11, the amount of formic acid 1.0mol (20.0M) being only added, Ir/L6=1/6 the results are shown in Table example 25 in 2.
Embodiment 26
Weigh [Cp*IrCl2]2(4.0mg, 5.0 μm of ol) and L7 (12 μm of ol) are put in a reagent bottle, and methanol is added
1.0mL is configured to the methanol solution of situ catalytic agent.Magneton, methanol is added into a Schlenk reaction tube or bottle
(9.42mL) and formic acid (10mmol, 0.38mL), is sealed, branch pipe connects rubber tube with rubber stopper；Reaction flask is put into 60 DEG C
After stirred in water bath stablizes 10min, the above-mentioned catalyst solution 0.2mL (1.0 μm of ol) prepared is pipetted with liquid-transfering gun and is rapidly joined
In reaction flask, reaction flask is sealed, the band tubing linked on branch pipe is passed through to the 500mL graduated cylinder for filling water handstand in basin at once
In, timing starts, and collects gas with drainage.The gas flow collected in the unit of account time calculates TON and TOF, V (CO2)=
Arrange volume/2 of water, the amount M (H of the substance of the formic acid of decomposition2)=V (H2)/24, specific data are shown in Table example 26 in 3.
Embodiment 27
With embodiment 26, methanol only is replaced with ethyl alcohol, the results are shown in Table example 27 in 3.
Embodiment 28
With embodiment 26, methanol only is replaced with acetone, the results are shown in Table example 28 in 3.
Embodiment 29
With embodiment 26, methanol only is replaced with dimethylformamide, the results are shown in Table example 29 in 3.
Embodiment 30
With embodiment 26, methanol only is replaced with dimethyl sulfoxide, the results are shown in Table example 30 in 3.
Embodiment 31
With embodiment 26, pure methanol only is replaced with the mixed solvent (v/v:1/1) of water and methanol, the results are shown in Table example in 3
31。
Embodiment 32
With embodiment 26, pure methanol only is replaced with the mixed solvent (v/v:1/1) of water and acetone, the results are shown in Table example in 3
32。
Table 1: the influence that ligand structure reacts formate dehydrogenasea
a:Reaction condition: [IrCp*Cl2]2(0.5 μm of ol), Ir/L=1/1.2, aqueous formic acid (1.0M, 10.0 mL),
60℃；If do not illustrated, what conversion ratio when TOF refers to latter 3 minutes by reaction calculated；b:Reaction starts to count
When also calculated without bubble, conversion ratio when with 20 minutes within 15 minutes；c:When TOF refers to latter 8 minutes by reaction
What conversion ratio calculated.
The influence that the amount of 2 ligand of table reacts formate dehydrogenasea
a:Reaction condition: generated in-situ catalyst is by [IrCp*Cl2]2It is generated before the reaction with L6, [IrCp*Cl2]2:
(0.5 μm of ol), formic acid (10.0M), 90 DEG C；b:Formic acid (12.0M)；c:70℃；d:L8 is as ligand；e:L8 is as ligand, and 70 DEG C
；f:L6 is as ligand, formic acid (15.0M)；g:L6 is as ligand, formic acid (20.0M).
Table 3: the influence that solvent reacts formate dehydrogenasea
a:Reaction condition: Ir-L7, the various solution (1.0M, 10.0mL) of formic acid, 60 DEG C；If do not illustrated, TOF is
Refer to what the conversion ratio by reaction at latter 3 minutes calculated.
Catalyst of the present invention includes metal and ligand, and metal is iridium, rhodium, ruthenium and cobalt etc., and ligand is the oxime ether that amino replaces
Class compound；Such catalyst is used for the dehydrogenation reaction of formic acid for the first time, and under the conditions of alkali-free, highest TON is up to 505 at 70 DEG C
×104, it is the peak reported at present, highest TON is up to 400 × 10 at 90 DEG C4, it is the peak reported at this temperature.
Claims (4)
1. one kind is used for the catalyst of formate dehydrogenase, which be can be by metal precursor and the generated in-situ metal network of ligand
Mixture catalyst, or it is also possible to the metal complex catalyst prepared；Metal precursor includes one in iridium, rhodium, ruthenium and cobalt
Kind or two kinds or more of metal salt；Ligand structure is one of as shown in A-D or two kinds or more, structure of metal complex such as E-G
It is one of shown or two kinds or more；
R is H or C1-18One of alkyl or two kinds or more；
N=0 or 1-4
R1=H or C1-18One of alkyl or Si (CH3)3, Si (C2H5)3, Si (CH2Ph)3One of or two kinds or more；
R2, R3, R4=H or C1-18One of alkyl or two kinds or more；
X is one of CH or N；
L1=cyclopentadienyl group (Cp), pentamethylcyclopentadiene base (Cp*), replace or one of unsubstituted aromatic rings or
Two kinds or more, aromatic rings is one of phenyl, naphthalene etc. or two kinds, and the substituent group number on aromatic rings can be 1-5, is replaced
Base can be one of methyl, ethyl, isopropyl or two kinds or more；
L2,L3,L4=Cl, CO, H2O,OH,CH3CN,N3, DMF, one of DMSO or two kinds or more；
One of M=iridium, rhodium, ruthenium and cobalt or two kinds or more；
A is the integer between 1 to 6；
V=0, one of+1 ,+2 ,+3 ,+4 ,+5 ,+6；
Be-For anion, Be-Concretely Cl-、Br-、I-、H-、BArF-、NO3 -、BF4 -、PF6 -、SO4 2-、CO3 2-、PO4 3With
CF3SO3 -One of, e charge number, specially 1, one in 2,3,4,5,6；
V=a × e.
2. a kind of application of the catalyst described in claim 1 in formate dehydrogenase, formic acid can be pure formic acid, or be also possible to
The mixed solution that formic acid and other solvents are formed, other solvents refer to water, acetone, methanol, ethyl alcohol, dimethylformamide and diformazan
One of sulfoxide etc. or two kinds or more.
3. the application of catalyst as claimed in claim 2, formic acid is dense in the mixed solution that the formic acid is formed with other solvents
Degree can be 0.001-25mol/L, and preferably 0.5-15mol/L is proper.
4. the application of catalyst as described in Claims 2 or 3, the reaction temperature is at 20-120 DEG C, preferably 40-100 DEG C ratio
Appropriate, catalyst concn is between 0.001-3.0mol/L, and preferably 0.05-1mol/L is proper.
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