CN108997435A - A kind of bipyridyl pyrroles-ruthenium (I) complex and preparation method thereof and application as electrochemical reduction catalyst - Google Patents

A kind of bipyridyl pyrroles-ruthenium (I) complex and preparation method thereof and application as electrochemical reduction catalyst Download PDF

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CN108997435A
CN108997435A CN201810527857.7A CN201810527857A CN108997435A CN 108997435 A CN108997435 A CN 108997435A CN 201810527857 A CN201810527857 A CN 201810527857A CN 108997435 A CN108997435 A CN 108997435A
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pdp
bipyridyl
ruthenium
pyrroles
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CN108997435B (en
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易小艺
肖会琼
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Central South University
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    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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Abstract

The invention discloses a kind of bipyridyl pyrroles-ruthenium (I) complex and preparation method thereof and as the application of electrochemical reduction catalyst, [Ru2(CO)4(PDP)2] complex is by 2,5- bipyridyl pyrroles and ten dicarbapentaborane, three ruthenium react to obtain in reflux in toluene, or by 2,5- bipyridyl pyrroles and dichloro dicarbapentaborane close ruthenium (II) polymer and acid binding agent, and back flow reaction obtains in methyl alcohol, its synthetic method step is simple, it is easily operated, mild condition, [the Ru of preparation2(CO)4(PDP)2] complex is as CO2The homogeneous catalyst of electrochemical catalysis reduction uses, and shows higher catalytic activity.

Description

A kind of bipyridyl pyrroles-ruthenium (I) complex and preparation method thereof and as electrochemistry The application of reducing catalyst
Technical field
The present invention relates to one kind [Ru2(CO)4(PDP)2] complex, it further relates to through the oxidation of ten dicarbapentaborane, three ruthenium or two Conjunction ruthenium (II) the polymer reduction of chlorine dicarbapentaborane is reacted with 2,5- bipyridyl pyrrole ligand (HPDP) prepares [Ru2(CO)4 (PDP)2] complex method, further relate to [Ru2(CO)4(PDP)2] complex is as CO2The homogeneous catalysis of electrochemical catalysis reduction The application of agent belongs to homogeneous catalysis technical field.
Background technique
[Ru2(CO)4]2+Complex is the substrate activated intermediate in homogeneous catalysis, such as CO2It is catalyzed the activity of reduction Intermediate.Chardon-Noblat et al. (Chardon-Noblat S, Deronzier A, Ziessel R, et al.Selective Synthesis and Electrochemical Behavior of trans(Cl)-and cis(Cl)- [Ru(bpy)(CO)2Cl2] Complexes (bpy=2,2 '-Bipyridine) .Comparative Studies of Their Electrocatalytic Activity toward the Reduction of Carbon Dioxide[J].Inorganic Chemistry, 1997,36 (23): 5384-5389.) discovery cis (Cl)-[Ru (bpy) (CO)2Cl2] and cis (CO)-[Ru (bpy)(CO)2(C (O) OMe) Cl] be all carbon dioxide electroreduction procatalyst.They propose, Cl-Leave away and lead to [Ru2 (CO)4]2+Formation, be catalyzed CO2It is reduced into the formates of CO and trace.Ishida is reported in DMA/H2In O mixture trans(Cl)-[Ru(bpy)(CO)2Cl2] and [Ru (bpy)3]2+Photosensitized reaction (Kuramochi Y, Itabashi J, Fukaya K,et al.Unexpected effect of catalyst concentration on photochemical CO2reduction by trans(Cl)–Ru(bpy)(CO)2Cl2:new mechanistic insight into the CO/ HCOO-selectivity[J].Chemical science,2015,6(5):3063-3074.).The ratio that CO and formates generate Example depends on catalyst concn and intensity of illumination.Author is by introducing [Ru2(CO)4]2+Formation explain this selectivity, [Ru2(CO)4]2+It is responsible for generating formic acid, while proposes that monokaryon catalyst generates CO.When catalyst concn increases, catalyst One electron reduction substance cannot obtain more electronics, and tendency generates [Ru2(CO)4]2+, CO/HCOO-Value reduces；Work as intensity of illumination When reduction, CO/HCOO-Value also reduces, and shows [Ru2(CO)4]2+As the critical active intermediate in catalytic cycle.In order to test This is demonstrate,proved it is assumed that author has synthesized trans- trans (Cl)-[Ru (Mesbpy) (CO)2Cl2], wherein [Ru2(CO)4]2+Formation Obstruction by the methyl group on bpy ligand.In this case, photocatalysis carbon dioxide reduction is selectively generating CO, The only formates of trace.Kubia confirmed [Ru when the electrochemical carbon dioxide for studying the catalyst restores in 20152 (CO)4]2+Inhibiting effect (Machan C W, Sampson M D, the Kubiak C P.A molecular ruthenium of formation electrocatalyst for the reduction of carbon dioxide to CO and formate[J] .Journal of the American Chemical Society,2015,137(26):8564-8571.).CO is that phenol is made For the primary product in the control potential electrolysis (CPE) of proton source, although selectivity of product is decided by use in this case Voltage.
In short, this kind of compound of the more pyridine Systems of ruthenium-is with synthesis Modulatory character, stability and to CO2Reduction catalysts are made High activity.But although more pyridines may to be synthesized modification various with various electronics and three-dimensional effect to provide Ligand, but see that so small variation is surprising in the structure of the ligand of most study, such as bipyridyl, phenanthrene are coughed up Quinoline and terpyridyl.Substituent group is normally limited to methyl, tert-butyl and carboxyl, this is because the fact, i.e., only it is a small number of this The derivative of sample can obtain on the market, and be used to prepare the original of bipyridyl, phenanthroline and terpyridine ligand in exploitation Effort in terms of the synthetic strategy of derivative is very little.Double-core Ru (I)-Ru (I) complex based on them mainly leads at present It crosses electrochemical means to synthesize, or the intermediate to be formed in optical electrical catalytic process, preparation method are more complex.
Summary of the invention
For drawbacks described above existing for the more pyridine Systems of ruthenium-in the prior art, the first purpose of this invention is to be It is good to provide a kind of stability, CO2High [the Ru of reducing catalysis action activity2(CO)4(PDP)2] complex.
For existing [Ru2(CO)4]2+Synthesis [the Ru of complex2(CO)4]2+There are energy consumption height, complicated for operation wait to lack for method Point, second object of the present invention are to be to provide a kind of synthesis [Ru2(CO)4(PDP)2] method, this method enriches [Ru2 (CO)4]2+Complex synthesis, step is simple, easily operated, is conducive to expanding production.
Third object of the present invention is to be [Ru2(CO)4(PDP)2] complex is as electrochemical reduction CO2Catalyst Application, show higher catalytic activity.
In order to achieve the above technical purposes, the present invention provides one kind [Ru2(CO)4(PDP)2] complex, with formula 1 Structure:
Wherein, R1And R2It is independently selected from hydrogen or halogen.
Preferably [Ru2(CO)4(PDP)2] complex is
The present invention also provides [Ru2(CO)4(PDP)2] complex synthetic method comprising following two synthetic method:
Scheme one: 2,5- bipyridyl pyrroles and ten dicarbapentaborane, three ruthenium reflux in toluene react to get；
Two: 2,5- bipyridyl pyrroles of scheme closes ruthenium (II) polymer with dichloro dicarbapentaborane and acid binding agent returns in methyl alcohol Stream reaction to get.
Preferred scheme, in scheme one, the mole of 2,5- bipyridyl pyrrole ligands is ten dicarbapentaborane, three ruthenium mole 3~4 times.
Preferred scheme, in scheme one, back flow reaction temperature is 110~120 DEG C, and the time is 8~12h.
Preferred scheme, in scheme two, the mole of 2,5- bipyridyl pyrrole ligands is that dichloro dicarbapentaborane closes ruthenium (II) 1~2 times of polymer mole.
Preferred scheme, in scheme two, the mole of acid binding agent is 3~4 times of 2,5- bipyridyl pyrroles's mole.It ties up Sour agent is triethylamine.
Preferred scheme, in scheme two, the temperature of back flow reaction is 70~90 DEG C, and the time is 8~12h.
The present invention also provides [Ru2(CO)4(PDP)2] complex application, as homogeneous catalyst be applied to CO2Electricity Chemical catalysis reduction.
[Ru of the invention2(CO)4(PDP)2] complex major ligand be 2,5- bipyridyl pyrroles, be a kind of more pyrroles Pyridine multidentate ligand has coordination mode abundant, can stable metal center improve urging for complex and by electronic effect Change activity.
[Ru of the invention2(CO)4(PDP)2] binuclear complex is as carbon dioxide reduction catalyst and other more pyridine rutheniums Carbonyl-complexes are compared, and containing Ru-Ru metallic bond, Ru is in+1 lower valency, are generated with the latter by reduction catalysts circulation [Ru2(CO)4]2+Double-core catalytic activity intermediate structure is similar, and theoretically reduzate HCOOH selectively will be higher, catalytic It can be more preferable.
The present invention [Ru2(CO)4(PDP)2] complex synthetic method, propose two kinds of synthesis thinkings.The first thinking Are as follows: using ten dicarbapentaborane, three ruthenium as precursor, with 2,5- bipyridyl pyrrole ligand (HPDP) in reflux in toluene, pass through ten dicarbapentaborane Three rutheniums aoxidize to obtain [Ru2(CO)4(PDP)2] complex；This method is dexterously on 2,5- bipyridyl pyrrole ligand (HPDP) Amide proton as oxidant, 0 valence ruthenium in ten dicarbapentaborane, three ruthenium is oxidized to+1 valence ruthenium.Second of thinking are as follows: by with 2,5- bipyridyl pyrrole ligand (HPDP) reaction reduction dichloro dicarbapentaborane in methanol in the presence of acid binding agent (triethylamine) The preparation of ruthenium (II) polymer is closed, complex [Ru is obtained2(CO)4(PDP)2]；Wherein there are two important role, a sides for methanol tool On the other hand face is used as reducing agent, precursor+divalent ruthenium is reduced to+1 valence ruthenium as solvent.
Ten dicarbapentaborane, three ruthenium:
2,5- bipyridyl pyrrole ligand:
[Ru2(CO)4(PDP)2] complex:
Wherein, R in structure above1For H, R2For H；Alternatively, R1For Cl, R2For H；Or R1For H, R2For Br.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1) [Ru of the invention2(CO)4(PDP)2] complex is using 2,5- bipyridyl pyrroles's multidentate ligand, with abundant Coordination mode, can stable metal center improve the catalytic activity of complex, and contain Ru-Ru gold and by electronic effect Belong to key, Ru is in+1 lower valency, and relatively existing similar complex has better stability and higher catalytic activity.
2) the invention proposes two kinds of completely new synthesis [Ru2(CO)4(PDP)2] complex method, by 2,5-, bis- pyridine Base pyrrole ligand (HPDP) is aoxidized with ten dicarbapentaborane, three ruthenium, or by 2,5- bipyridyl pyrrole ligand (HPDP) and dichloro Dicarbapentaborane closes ruthenium (II) polymer and obtains [Ru through reduction2(CO)4]2+Complex.Simple with step, reaction condition is mild, easily In operation the advantages that, be conducive to large-scale production and application.
3) [Ru of the invention2(CO)4(PDP)2] complex as homogeneous catalyst, matches compared to other monokaryons Ru (II) Object is closed, containing Ru (I)-Ru (I) metallic bond, stability is preferable, shows higher CO2Electrochemical catalysis reducing property, has Wide application prospect.
Detailed description of the invention
[Fig. 1] is 1 [Ru of complex in embodiment 12(CO)4(L1)2]1H NMR spectra；
[Fig. 2] is 1 [Ru of complex in embodiment 12(CO)4(L1)2] IR map；
[Fig. 3] is 1 [Ru of complex in embodiment 12(CO)4(L1)2] mono-crystalline structures ellipsoid figure；
[Fig. 4] is 2 [Ru of complex in embodiment 32(CO)4(L2)2]1H NMR spectra；
[Fig. 5] is 2 [Ru of complex in embodiment 32(CO)4(L2)2] IR map；
[Fig. 6] is 2 [Ru of complex in embodiment 32(CO)4(L2)2] mono-crystalline structures ellipsoid figure；
[Fig. 7] is 3 [Ru of complex in embodiment 42(CO)4(L3)2]1H NMR spectra；
[Fig. 8] is 3 [Ru of complex in embodiment 42(CO)4(L3)2] IR map；
[Fig. 9] is 3 [Ru of complex in embodiment 42(CO)4(L3)2] mono-crystalline structures ellipsoid figure；
[Figure 10] is ultraviolet-visible spectrogram of the complex 1~3 in dichloromethane solution in Examples 1 to 4；
[Figure 11] is complex 1 in embodiment 5 in Ar and CO2Electrochemistry cyclic voltammetry curve figure under atmosphere；
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention It encloses.
Compound in following embodiment does not have specified otherwise such as, and raw material is marketable material.
Examples 1 to 4 and comparative example 1~3 mainly illustrate [Ru2(CO)4(PDP)2] complex synthesis.
Embodiment 5 mainly illustrates [Ru2(CO)4(PDP)2] as homogeneous catalyst catalysis CO2The property of electrochemical reduction.
Substrate raw material and solvent etc. involved in following embodiment are commercially available commercial product (analytical reagents), institute With reagent by purifying, dry and deoxygenation pretreatment, the synthesis being related to and treatment process use standard anhydrous and oxygen-free technology.Its Middle dichloro dicarbapentaborane closes ruthenium (II) polymer (Anderson P A, Deacon G B, Haarmann K H, et al.Designed synthesis of mononuclear tris(heteroleptic)ruthenium complexes containing bidentate polypyridyl ligands[J].Inorganic Chemistry,1995,34(24): 6145-6157.) and 2,5- bipyridyl pyrroles (HPDP) (Imler G H, Lu Z, Kistler K A, et al.Complexes of 2,5-Bis(α-pyridyl)pyrrolate with Pd(II)and Pt(II):A Monoanionic Iso-π-Electron Ligand Analog of Terpyridine[J].Inorganic Chemistry, 2012,51 (19): 10122-10128.) it is synthesized by the method that has been reported.
1H NMR (400MHz), with CDCl3For solvent, using TMS as internal standard.
Multiplicity is defined as follows: s (unimodal)；D (doublet)；T (triplet)；Q (quartet) and m (multiplet).Coupling Constant J (hertz).
IR, KBr tabletting.Absorption intensity is defined as follows: s (strong to absorb)；M (moderate absorption)；W (weak absorbing).
Synthetic method one:
Under nitrogen atmosphere, by ligand 2,5- bipyridyl pyrroles (HPDP) (2.4mmol) and Ru3(CO)12(0.6mmol) It is placed in two mouthfuls of round-bottomed flasks of 100mL, the toluene (40mL) of abundant deoxygenation is added, is heated to flowing back under stirring, Ru3(CO)12 It gradually dissolves, obtains peony clear solution.It is persistently stirred at reflux overnight, there is the generation of yellow insoluble matter, reaction is completed.Wait react After system is cooled to room temperature, removed by filtration solution collects yellow mercury oxide, respectively with cold toluene (5mL*3) and ether (5mL*3) It washs, it is dry under vacuum, obtain product.
Synthetic method two:
Under nitrogen atmosphere, by ligand 2,5- bipyridyl pyrroles (HPDP) (1mmol) and polymer [RuCl2(CO)2]n (1mmol) is placed in two mouthfuls of round-bottomed flasks of 50mL, and the methanol (30mL) of abundant deoxygenation, dried triethylamine is added (3.6mmol) is used as deprotonation alkali.Reaction mixture is heated to flowing back with stirring, and solid, which gradually dissolves, obtains brownish red clarification Solution.It is persistently stirred at reflux overnight, there is the generation of yellow insoluble matter, reaction is completed.After reaction system is cooled to room temperature, after filtering Yellow mercury oxide is obtained, is washed respectively with cold methanol (5mL*3) and ether (5mL*3), is drained, obtain product.
It is reacted according to above-mentioned reaction condition following example 1~4:
Embodiment 1
It is synthesized by method one:
Raw material: 2,5- bipyridyl pyrroles (HL1), ten dicarbapentaborane, three ruthenium；
Target product:1 [Ru of complex2(CO)4(L1)2]；Yield: 68%；
1H NMR(400MHz,CDCl3): δ 8.65 (d, J=5.04Hz, 2H), 8.58 (dd, J=5.84,1.08Hz, 2H), 7.43 (td, J=8.24,1.52Hz, 2H), 7.30 (d, J=7.68Hz, 2H), 7.23 (td, J=7.04,1.60Hz, 2H), 7.12 (d, J=8.16Hz, 2H), 6.97 (td, J=5.48,1.12Hz, 2H), 6.53 (q, J=3.92Hz, 4H), 6.42 (td, J=7.20,1.52Hz, 2H)；
IR(KBr,cm-1):2010(s),1967(s),1925(s),1600(m),1552(w),1505(m),1456(w), 1429(m),1339(m),1157(w),963(w),780(w),746(m),650(w),586(w),538(w)。
Embodiment 2
It is synthesized by method two:
Raw material: 2,5- bipyridyl pyrroles (HL1), [Ru (CO)2Cl2]n, triethylamine；
Target product:1 [Ru of complex2(CO)4(L1)2]；Yield: 39%；
Characterize data is the same as embodiment 1 in method one.
Embodiment 3
It is synthesized by method two:
Raw material: the chloro- 2,5- bipyridyl pyrroles (HL of 3,4- bis-2),[Ru(CO)2Cl2]n, triethylamine；
Target product:2 [Ru of complex2(CO)4(L2)2]；Yield: 35%；
1H NMR(400MHz,CDCl3): δ 8.77 (d, J=4.84Hz, 2H), 8.65 (dd, J=5.84,0.96Hz, 2H), 7.87 (d, J=8.24Hz, 2H), 7.81 (d, J=8.24Hz, 2H), 7.56 (td, J=7.24,1.36Hz, 2H), 7.45 (td, J=8.68,1.64Hz, 2H), 7.09 (td, J=5.52,1.04Hz, 2H), 6.67 (td, J=8.76,1.52Hz, 2H)；
IR(KBr,cm-1):2016(s),1970(s),1936(s),1915(s),1597(s),1556(w),1492(m), 1432(m),1336(s),1159(w),972(w),776(w),744(w),647(w),571(w),533(w)。
Embodiment 4
It is synthesized by method two:
Raw material: 2,5- bis- (5,5 '-dibromo) Pyridylpyrrole (HL3), [Ru (CO)2Cl2]n, triethylamine；
Target product:3 [Ru of complex2(CO)4(L3)2]；
Yield: 25%；
1H NMR(400MHz,CDCl3): δ 8.74 (d, J=1.92Hz, 2H), 8.60 (d, J=2.12Hz, 2H), 7.61 (dd, J=8.64,2.04Hz, 2H), 7.33 (dd, J=8.84,2.20Hz, 2H), 7.16 (d, J=8.88Hz, 2H), 7.04 (d, J=8.64Hz, 2H), 6.51 (d, J=3.76Hz, 2H), 6.48 (d, J=3.88Hz, 2H)；
IR(KBr,cm-1):2021(s),1977(s),1927(s),1583(m),1504(s),1444(m),1369(s), 1327(m),1230(w),1140(w),918(w),827(w),760(w),729(w),650(w),588(w),534(w)。
Embodiment 5
Take 3.7mg [Ru2(CO)4(L1)2] (the ammonium hexafluorophosphate of the tetrabutyl containing 0.1M conduct support is dissolved in 5mL acetonitrile solution Electrolyte), it is configured to 1mM complex solution, carries out cyclic voltammetry.Test uses three-electrode system, and glass-carbon electrode is work Make electrode, platinum electrode is to electrode, Ag/AgNO3Electrode is as reference electrode.Cyclic voltammetry is respectively at inert atmosphere (Ar) and CO2It is carried out under atmosphere.
When replacing for other compared with macoradical or different location in order to illustrate substituent group, it is difficult to the case where obtaining complex, The 2,5- bipyridyl pyrrole ligand that uses other to replace compared with macoradical or different location synthesizes mesh with two similarity condition of method Mark complex [Ru2(CO)4(PDP)2], see comparative example 1~3.
Comparative example 1
It is synthesized by method two:
Raw material: 2,5- bis- (6,6 '-dibromo) Pyridylpyrrole (HL4),[Ru(CO)2Cl2]n, triethylamine；
2,5- bis- (6,6 '-dibromo) Pyridylpyrrole (HL4):
Title complex is not obtained.
Comparative example 2
It is synthesized by method two:
Raw material: 2,5- bis- (5,5 '-diphenyl) Pyridylpyrrole (HL5),[Ru(CO)2Cl2]n, triethylamine；
2,5- bis- (5,5 '-diphenyl) Pyridylpyrrole (HL5):
Title complex is not obtained.
Comparative example 3
It is synthesized by method two:
Raw material: 2,5- bis- (5,5 '-Dithiophene) Pyridylpyrrole (HL6),[Ru(CO)2Cl2]n, triethylamine；
2,5- bis- (5,5 '-Dithiophene) Pyridylpyrrole (HL6):
Title complex is not obtained.
FIG. 1 to FIG. 9 is respectively the nuclear-magnetism of complex 1~3, infrared, mono-crystalline structures；Figure 10 is that the ultraviolet of complex 1~3 can Light-exposed spectrogram；Figure 11 illustrates complex 1 in Ar and CO2Cyclic voltammetry curve figure under atmosphere, there it can be seen that Epa=- Reduction peak current at 2.50V is in CO2Have under atmosphere compared to Ar atmosphere and significantly increase, is carbon dioxide reduction process, explanation Complex 1 is to CO2Electrochemical catalysis reduction has greater activity.
The crystallographic data table of complex 1~3 in 1 Examples 1 to 4 of table
Part bond distance's bond angle data of complex 1~3 in 2 Examples 1 to 4 of table
The present invention has been shown and described above and prepares [Ru2(CO)4]2+The main method feature and advantage of complex.Current row The technical staff of industry is it should be appreciated that the present invention is not limited to the above embodiments, and described in the above embodiment and specification It is to illustrate the principle of the present invention and method process, without departing from the spirit and scope of the present invention, the present invention also has respectively Kind changes and improvements, these changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by Appended claims and its equivalent thereof.

Claims (9)

1. one kind [Ru2(CO)4(PDP)2] complex, it is characterised in that: there is 1 structure of formula:
Wherein, R1And R2It is independently selected from hydrogen or halogen.
2. one kind [Ru according to claim 12(CO)4(PDP)2] complex, it is characterised in that: it is
3. [Ru of any of claims 1 or 22(CO)4(PDP)2] complex synthetic method, it is characterised in that:
Scheme one: 2,5- bipyridyl pyrroles and ten dicarbapentaborane, three ruthenium reflux in toluene react to get；
Two: 2,5- bipyridyl pyrroles of scheme and dichloro dicarbapentaborane close ruthenium (II) polymer and acid binding agent flows back instead in methyl alcohol It should be to get.
4. [Ru according to claim 32(CO)4(PDP)2] complex synthetic method, it is characterised in that: in scheme one, The mole of 2,5- bipyridyl pyrrole ligand is 3~4 times of ten dicarbapentaborane, three ruthenium mole.
5. [Ru according to claim 3 or 42(CO)4(PDP)2] complex synthetic method, it is characterised in that: scheme one In, back flow reaction temperature is 110~120 DEG C, and the time is 8~12h.
6. [Ru according to claim 32(CO)4(PDP)2] complex synthetic method, it is characterised in that: in scheme two, The mole of 2,5- bipyridyl pyrrole ligand is 1~2 times that dichloro dicarbapentaborane closes ruthenium (II) polymer mole.
7. [Ru according to claim 32(CO)4(PDP)2] complex synthetic method, it is characterised in that: in scheme two, The mole of acid binding agent is 3~4 times of 2,5- bipyridyl pyrroles's mole；The acid binding agent is triethylamine.
8. according to [Ru described in claim 3,6 or 72(CO)4(PDP)2] complex synthetic method, it is characterised in that: scheme In two, the temperature of back flow reaction is 70~90 DEG C, and the time is 8~12h.
9. [Ru of any of claims 1 or 22(CO)4(PDP)2] complex application, it is characterised in that: as homogeneous catalyst Applied to CO2Electrochemical catalysis reduction.
CN201810527857.7A 2018-05-29 2018-05-29 Dipyridyl pyrrole-ruthenium (I) complex, preparation method thereof and application thereof as electrochemical reduction catalyst Expired - Fee Related CN108997435B (en)

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Publication number Priority date Publication date Assignee Title
CN114478648A (en) * 2021-12-22 2022-05-13 中南大学 Pyridine-like pyrrole ruthenium complex, preparation method thereof and application of complex as electrocatalytic ammonia oxidation catalyst

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114478648A (en) * 2021-12-22 2022-05-13 中南大学 Pyridine-like pyrrole ruthenium complex, preparation method thereof and application of complex as electrocatalytic ammonia oxidation catalyst
WO2023116540A1 (en) * 2021-12-22 2023-06-29 中南大学 Pyridine pyrrole ruthenium complex, preparation method therefor and application thereof as catalyst for preparing hydrazine by electrocatalytic ammonia oxidation
CN114478648B (en) * 2021-12-22 2024-01-30 中南大学 Pyridine pyrrole ruthenium-like complex, preparation method thereof and application of pyridine pyrrole ruthenium-like complex as electrocatalytic ammoxidation catalyst

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