CN109575087A - The sandwich complex of iridium of double-core half of the ligand containing diimine, preparation method and applications - Google Patents
The sandwich complex of iridium of double-core half of the ligand containing diimine, preparation method and applications Download PDFInfo
- Publication number
- CN109575087A CN109575087A CN201811625370.9A CN201811625370A CN109575087A CN 109575087 A CN109575087 A CN 109575087A CN 201811625370 A CN201811625370 A CN 201811625370A CN 109575087 A CN109575087 A CN 109575087A
- Authority
- CN
- China
- Prior art keywords
- iridium
- double
- reaction
- diimine
- sandwich complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- 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
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention belongs to synthesising chemical technology field, the sandwich complex of iridium of double-core half of specially a kind of ligand containing diimine, preparation method and applications.The present invention is with pentamethylcyclopentadiene base iridium chloride dimer [(C5Me5)IrCl2]2For raw material, it is reacted under alkaline condition with the ligand of diimine containing pyrrole ring, prepares final N, the sandwich complex of iridium of double-core half of N- coordination.Synthesis technology of the present invention is simply green, has excellent selectivity and higher yields.The sandwich complex of iridium of double-core half of the invention has many characteristics, such as to stablize physicochemical properties and thermal stability, and efficient catalytic activity is shown in the reaction that halogenated hydrocarbons is oxidized to corresponding aldehyde.
Description
Technical field
The invention belongs to synthesising chemical technology fields, and in particular to a kind of sandwich iridium of double-core half cooperation of the ligand containing diimine
Object, preparation method and applications.
Background technique
Aldehyde is a kind of important organic compound, it is widely used in wood-processing industry, textile industry, health care, stone
The various fields such as oily exploitation, leather tanning.As the continuous development of each industry in China is grown, to the demand of aldehyde and its derivative
It also can be increasing.And aldehyde compound is also a kind of important organic synthesis intermediate, and aldehyde radical can be changed by reaction
At classes of compounds such as carboxylic acid, alcohol, amine.Currently, the method for synthesis aldehyde has very much, as alcohols prepares aldehyde, acids through also through oxidation
Original prepares aldehyde, olefines and through oxidation prepares aldehyde (this method usually requires strong acidic environment, the high requirements on the equipment and can generate big
Measure acid waste water) etc., but it is also seldom using the research that halogenated hydrocarbons prepares aldehyde for raw material direct oxidation, it is usually all first to be hydrolyzed
For alcohol, it is further oxidized to corresponding aldehyde, additional waste water and dregs will be generated in synthesis process per more steps, and final
The yield of product can also be declined.
Summary of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to propose that the double-core of a kind of ligand containing diimine half presss from both sides
Heart complex of iridium, preparation method and applications.Preparation method of the present invention is simply green, and the sandwich complex of iridium of half obtained can be with sky
Gas is oxidant, the direct halogenated oxidation reactions of hydrocarbons synthesizing aldehyde compound of efficient catalytic, can catalysis substrate type it is more, universality
It is good, higher catalytic activity is all had for the substrate of different electronic effects and space steric effect, reaction condition is mild, catalysis
High-efficient, cost is relatively low and product is easily isolated, and post-processing is simple, will not generate a large amount of waste residues, have broad application prospects.
Technical solution of the present invention is specifically described as follows.
The present invention provides a kind of sandwich complex of iridium of double-core half of ligand containing diimine, is used as efficient catalytic halogenated hydrocarbons oxygen
Change the catalyst of reaction synthesizing aldehyde compound, there is structure as follows:
The present invention also provides a kind of preparation methods of the sandwich complex of iridium of double-core half of ligand containing diimine, and specific steps are such as
Under:
- 78 DEG C at a temperature of, the hexane solution of n-BuLi is added drop-wise to the tetrahydro furan of the ligand of diimine containing pyrrole ring
It mutters in solution, continues stirring 30-60 minutes after completion of dropwise addition, be slowly increased to after room temperature be added five after the reaction was continued 30-60 minutes
Methyl cyclopentadienyl iridium chloride dimer [(C5Me5)IrCl2]2, continue to react 2.0~5.0 hours at room temperature；Reaction knot
Shu Hou, stands filtering, decompressing and extracting solvent, and obtained crude product carries out column chromatography for separation and obtains orange-red target product.
In the present invention, n-BuLi, the ligand of diimine containing pyrrole ring and [(C5Me5)IrCl2]2Molar ratio be (2.2~
2.8):1:0.9。
In the present invention, the eluant, eluent that column chromatography for separation is used is petroleum ether and dichloromethane of the volume ratio between 8:1~5:1
The mixed solvent of alkane composition.
It is halogenated in catalysis that the present invention further provides a kind of sandwich complex of iridium of double-core half of above-mentioned ligand containing diimine
Application in oxidation reactions of hydrocarbons synthesizing aldehyde compound.
In the present invention, the primary halogenated hydrocarbons for using alkyl, alkoxy, nitro or aryl to replace in halogenated oxidation reactions of hydrocarbons is original
Material.
In the present invention, the oxidant in halogenated oxidation reactions of hydrocarbons is air.
In the present invention, concrete application method is as follows: according to feeding intake for the primary halogenated hydrocarbons of raw material and the sandwich complex of iridium of double-core half
Molar ratio is 1000:1~500:1, the DMSO solution of the sandwich complex of iridium containing double-core half is added into primary halogenated hydrocarbons, 25~60
It is reacted 180~360 minutes at a temperature of DEG C, reaction solution is through washing, extraction and concentration after reaction, and crude product is through silica gel column layer
Analysis separation, obtains corresponding aldehyde compound.
Compared to the prior art, the beneficial effects of the present invention are,
(1) the sandwich complex of iridium preparation method of double-core half of the ligand containing diimine is simple in the present invention, has higher yields；
(2) present invention in the ligand containing diimine the sandwich complex of iridium thermal stability with higher of double-core half, at 300 DEG C
Under do not decompose still；
(3) trivalent iridium group with imine moiety of the invention, the alkene hydrogen amine with higher under conditions of mild (25-60 DEG C)
Change the catalytic activity of reaction, high income (87%~99%), reaction raw materials are (oxidant is air) cheap and easy to get, and regional choice
Property it is high, by-product is few.
Detailed description of the invention
Fig. 1 is the crystal structure of the sandwich complex of iridium of double-core half for the ligand containing diimine that embodiment 1 obtains.
Fig. 2 is the thermogravimetric curve of the sandwich complex of iridium of double-core half for the ligand containing diimine that embodiment 1 obtains.
Specific embodiment
The present invention is further specifically described below by embodiment, the present invention is not limited to the following examples.
Embodiment 1: the synthesis of the sandwich complex of iridium of double-core half of the ligand containing diimine
- 78 DEG C at a temperature of, the hexane solution (1.0mL, 1.6mmol) of n-BuLi (1.6M) is added drop-wise to containing pyrroles
Ring diimine ligand C10H10N4Continue 50 points of stirring in the tetrahydrofuran solution of (119.0mg, 0.64mmol), after completion of dropwise addition
Clock, is slowly increased to after room temperature that the reaction was continued is added pentamethylcyclopentadiene base iridium chloride dimer [Cp after sixty minutes*IrCl2]2
(460.0mg, 0.58mmol) continues to react 4 hours at room temperature；After reaction, filtering is stood, decompressing and extracting solvent obtains
To crude product carry out column chromatography for separation (petroleum ether/methylene chloride (v/v)=6:1) obtain orange-red target product
C30H38Cl2Ir2N4(437.0mg, yield 83%).Its crystal structure figure is as shown in Figure 1.Single crystal cultivation mode: purifying is obtained
Complex of iridium 20mg is dissolved in 5mL methylene chloride, and n-hexane is slowly diffused into the two of compound using liquid phase diffusion method
In chloromethanes solution, complex of iridium monocrystalline was precipitated at 3-5 days or so.
1H NMR(400MHz,CDCl3, 25 DEG C): δ 8.60 (s, 2H), 7.21 (s, 2H), 6.79 (d, J=3.5Hz, 2H),
6.38 (t, J=3.0Hz, 2H), 1.75 (s, 30H) .IR (KBr, disk): υ 3447,1610,1580,1427,1380,1280,
830. Elemental Analysis theories: C 39.60, H 4.60, N 6.17；Experiment value: C 39.69, H 4.60, N 6.16.
The sandwich complex of iridium of double-core half of diimine ligand is heated to reflux three hours in toluene solution, reacts cooling and takes out
Dry solvent, obtained solid carry out nuclear-magnetism characterization, and each nuclear magnetic signal is unchanged.In addition, weighing 4.0mg compound carries out thermogravimetric reality
It tests, compound is still stable (thermogravimetric curve is as shown in Figure 2) under 300 DEG C of high temperature as the result is shown.
Embodiment 2: the sandwich complex of iridium of the double-core half catalysis halogenated hydrocarbons of the ligand containing diimine is oxidized to aldehyde
Using embodiment 1 prepare catalyst halogenated hydrocarbons oxidation reaction: to bromoethane (1mmol, 109mg) and in
The DMSO solution of the half sandwich complex of iridium (0.001mmol, 0.9mg) Han double-core is added, opening is reacted, and 30 DEG C of reaction temperature, instead
It is 270 minutes between seasonable, reaction solution is separated through washing, extraction and concentration, crude product through silica gel column chromatography after reaction, dry
To mass conservation, corresponding aldehyde compound C is obtained2H4O (41mg, yield 93%), elemental analysis: the C 54.53, (reason of H 9.15
By)；C 54.43, H 9.19 (reality).
Embodiment 3: the sandwich complex of iridium of the double-core half catalysis halogenated hydrocarbons of the ligand containing diimine is oxidized to aldehyde
Using embodiment 1 prepare catalyst halogenated hydrocarbons oxidation reaction: to chloropropane (1mmol, 80mg) and in
The DMSO solution of the half sandwich complex of iridium (0.001mmol, 0.9mg) Han double-core is added, opening is reacted, and 50 DEG C of reaction temperature, instead
It is 300 minutes between seasonable, reaction solution is separated through washing, extraction and concentration, crude product through silica gel column chromatography after reaction, dry
To mass conservation, corresponding aldehyde compound C is obtained3H6O (55mg, yield 95%), elemental analysis: C 62.04, H 10.41
(theory)；C 62.03, H 10.53 (reality).
Embodiment 4: the sandwich complex of iridium of the double-core half catalysis halogenated hydrocarbons of the ligand containing diimine is oxidized to aldehyde
Using embodiment 1 prepare catalyst halogenated hydrocarbons oxidation reaction: to 2- nitro chloropropane (1mmol,
123mg) and temperature is reacted in the middle DMSO solution that the half sandwich complex of iridium (0.002mmol, 1.8mg) Han double-core is added, opening reaction
60 DEG C of degree, reaction time are 360 minutes, and reaction solution is through washing, extraction and concentration after reaction, and crude product is through silica gel column chromatography
Separation, it is dry to mass conservation, obtain corresponding aldehyde compound C3H5NO3(89mg, yield 87%), elemental analysis: C
34.96, H 4.89, N 13.59 (theory)；C 34.89, H 4.83, N 13.56 (reality).
Embodiment 5: the sandwich complex of iridium of the double-core half catalysis halogenated hydrocarbons of the ligand containing diimine is oxidized to aldehyde
Using embodiment 1 prepare catalyst halogenated hydrocarbons oxidation reaction: to 3- methoxyl group chloropropane (1mmol,
108mg) and temperature is reacted in the middle DMSO solution that the half sandwich complex of iridium (0.001mmol, 0.9mg) Han double-core is added, opening reaction
30 DEG C of degree, reaction time are 240 minutes, and reaction solution is through washing, extraction and concentration after reaction, and crude product is through silica gel column chromatography
Separation, it is dry to mass conservation, obtain corresponding aldehyde compound C4H8O2(83mg, yield 95%), elemental analysis: C
54.53, H 9.15 (theory)；C 54.57, H 9.22 (reality).
Embodiment 6: the sandwich complex of iridium of the double-core half catalysis halogenated hydrocarbons of the ligand containing diimine is oxidized to aldehyde
The oxidation reaction of the catalyst halogenated hydrocarbons prepared using embodiment 1: to benzyl chloride (1mmol, 126mg) He Zhongjia
Enter the DMSO solution of the half sandwich complex of iridium (0.001mmol, 0.9mg) Han double-core, opening reaction, is reacted by 25 DEG C of reaction temperature
Time is 180 minutes, and reaction solution is separated through washing, extraction and concentration, crude product through silica gel column chromatography after reaction, and drying is extremely
Mass conservation obtains corresponding aldehyde compound C7H6O (105mg, yield 99%), elemental analysis: the C 79.22, (reason of H 5.70
By)；C 79.18, H 5.76 (reality).
Claims (9)
1. a kind of sandwich complex of iridium of double-core half of ligand containing diimine, which is characterized in that it is used as catalysis halogenated hydrocarbons and is oxidized to
The catalyst of aldehyde reaction, with structure as follows:
2. a kind of preparation method of the sandwich complex of iridium of double-core half of the ligand according to claim 1 containing diimine, special
Sign is, the specific steps are as follows:
- 78 DEG C at a temperature of, the tetrahydrofuran that the hexane solution of n-BuLi is added drop-wise to the ligand of diimine containing pyrrole ring is molten
Continue stirring 30-60 minutes in liquid, after completion of dropwise addition, is slowly increased to after room temperature that pentamethyl is added after the reaction was continued 30-60 minutes
Cyclopentadienyl group iridium chloride dimer [(C5Me5)IrCl2]2, continue to react 2.0~5.0 hours at room temperature；After reaction,
Filtering, decompressing and extracting solvent are stood, obtained crude product carries out column chromatography for separation and obtains orange-red target product.
3. preparation method according to claim 2, which is characterized in that n-BuLi, the ligand of diimine containing pyrrole ring and
[(C5Me5)IrCl2]2Molar ratio be (2.2~2.8): 1:0.9.
4. preparation method according to claim 2, which is characterized in that the eluant, eluent that column chromatography for separation is used is that volume ratio exists
The mixed solvent of petroleum ether and methylene chloride composition between 8:1~5:1.
5. a kind of sandwich complex of iridium of double-core half of the ligand according to claim 1 containing diimine is as catalyst halogenated
Hydrocarbon is oxidized to the application in aldehyde reaction.
6. application according to claim 5, which is characterized in that halogenated hydrocarbons is oxidized in aldehyde reaction, use primary halogenated hydrocarbons for
Raw material.
7. application according to claim 5 or 6, which is characterized in that halogenated hydrocarbons is oxidized in aldehyde reaction using alkyl, alcoxyl
The primary halogenated hydrocarbons that base, nitro or aryl replace is raw material.
8. application according to claim 5, which is characterized in that it is air that halogenated hydrocarbons, which is oxidized to the oxidant in aldehyde reaction,.
9. application according to claim 5, which is characterized in that concrete application method is as follows: according to the primary halogenated hydrocarbons of raw material and
The molar ratio of the sandwich complex of iridium of double-core half of the ligand containing diimine is 1000:1~500:1, is added into primary halogenated hydrocarbons
The DMSO solution of the sandwich complex of iridium of double-core half of the ligand containing diimine, in 25~60 DEG C of at a temperature of 180~360 points of reaction
Clock, reaction solution is separated through washing, extraction and concentration, crude product through silica gel column chromatography after reaction, obtains corresponding aldehydes
Close object.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811625370.9A CN109575087B (en) | 2018-12-28 | 2018-12-28 | Binuclear half-sandwich iridium complex containing diimine ligand, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811625370.9A CN109575087B (en) | 2018-12-28 | 2018-12-28 | Binuclear half-sandwich iridium complex containing diimine ligand, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109575087A true CN109575087A (en) | 2019-04-05 |
| CN109575087B CN109575087B (en) | 2020-12-08 |
Family
ID=65932216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811625370.9A Active CN109575087B (en) | 2018-12-28 | 2018-12-28 | Binuclear half-sandwich iridium complex containing diimine ligand, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109575087B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105404A (en) * | 2019-05-07 | 2019-08-09 | 上海应用技术大学 | The ruthenium complex of the benzoxazoles structure of carborane radical containing ortho position and its preparation and application |
| CN110117299A (en) * | 2019-05-30 | 2019-08-13 | 上海应用技术大学 | The rhodium complex of the benzimidazole structure of carborane radical containing ortho position and its preparation and application |
| CN110201720A (en) * | 2019-06-12 | 2019-09-06 | 上海应用技术大学 | A kind of application of double-core rhodium complex in fatty amine N- methylation reaction |
| CN110483581A (en) * | 2019-08-09 | 2019-11-22 | 上海应用技术大学 | It is a kind of containing the palladium complex of carborane ligand and its preparation and application between double phosphines |
| CN111454296A (en) * | 2020-04-07 | 2020-07-28 | 上海应用技术大学 | Palladium complex containing m-carborane triazole ligand and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000040528A1 (en) * | 1999-01-06 | 2000-07-13 | Univation Technologies, Llc | Pentafulvene synthesis |
| US6737531B1 (en) * | 2002-12-17 | 2004-05-18 | Brookhaven Science Associates, Llc | Catalysts for hydrogenation and hydrosilylation, methods of making and using the same |
| US20050075504A1 (en) * | 2002-12-17 | 2005-04-07 | Dioumaev Vladimir K. | Recyclable catalysts methods of making and using the same |
| CN102432640A (en) * | 2011-10-09 | 2012-05-02 | 复旦大学 | Half-sandwiched iridium (Ir) and rhodium (Rh) compound having carborane-amidine-containing structure, and preparation method and application of half-sandwiched Ir and Rh compound |
| JP2017014195A (en) * | 2015-06-26 | 2017-01-19 | 日本曹達株式会社 | Iridium complex |
| CN106589002A (en) * | 2016-12-07 | 2017-04-26 | 上海应用技术大学 | Half-sandwich iridium and rhodium compound with aryl structure as well as preparation method and application of half-sandwich iridium and rhodium compound |
-
2018
- 2018-12-28 CN CN201811625370.9A patent/CN109575087B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000040528A1 (en) * | 1999-01-06 | 2000-07-13 | Univation Technologies, Llc | Pentafulvene synthesis |
| US6737531B1 (en) * | 2002-12-17 | 2004-05-18 | Brookhaven Science Associates, Llc | Catalysts for hydrogenation and hydrosilylation, methods of making and using the same |
| US20050075504A1 (en) * | 2002-12-17 | 2005-04-07 | Dioumaev Vladimir K. | Recyclable catalysts methods of making and using the same |
| CN102432640A (en) * | 2011-10-09 | 2012-05-02 | 复旦大学 | Half-sandwiched iridium (Ir) and rhodium (Rh) compound having carborane-amidine-containing structure, and preparation method and application of half-sandwiched Ir and Rh compound |
| JP2017014195A (en) * | 2015-06-26 | 2017-01-19 | 日本曹達株式会社 | Iridium complex |
| CN106589002A (en) * | 2016-12-07 | 2017-04-26 | 上海应用技术大学 | Half-sandwich iridium and rhodium compound with aryl structure as well as preparation method and application of half-sandwich iridium and rhodium compound |
Non-Patent Citations (5)
| Title |
|---|
| DAVID L. DAVIES等，: "N-H versus C-H Activation of a Pyrrole Imine at {Cp*Ir}: A Computational and Experimental Study", 《ORGANOMETALLICS》 * |
| H. BRUNNER等，: "Optically active transition metal complexes Part 125. Preparation and epimerization of chiral-at-metal pentamethylcyclopentadienyl-rhodium(III) and iridium(III) half-sandwich complexes", 《POLYHEDRON》 * |
| HENRI BRUNNER等，: "Optically active transition metal complexes. Part 133 Preparation, epimerization and crystallization of chiral-at-metal rhodium(III) half-sandwich complexes", 《POLYHEDRON》 * |
| MANISH CHANDRA等，: "Synthetic, spectral and structural aspects of some Rh(III) pentamethylcyclopentadiene complexes containing N,N-donor bridging ligands", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| ZHUO WANG等，: "Facile and practical synthesis of β-carbolinium salts and γ-carbolinium salts via rhodium rhodiumcatalyzed", 《ORG. BIOMOL. CHEM.》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105404A (en) * | 2019-05-07 | 2019-08-09 | 上海应用技术大学 | The ruthenium complex of the benzoxazoles structure of carborane radical containing ortho position and its preparation and application |
| CN110117299A (en) * | 2019-05-30 | 2019-08-13 | 上海应用技术大学 | The rhodium complex of the benzimidazole structure of carborane radical containing ortho position and its preparation and application |
| CN110117299B (en) * | 2019-05-30 | 2021-05-11 | 上海应用技术大学 | Rhodium complex containing ortho-carbon boron alkyl benzimidazole structure and preparation and application thereof |
| CN110201720A (en) * | 2019-06-12 | 2019-09-06 | 上海应用技术大学 | A kind of application of double-core rhodium complex in fatty amine N- methylation reaction |
| CN110483581A (en) * | 2019-08-09 | 2019-11-22 | 上海应用技术大学 | It is a kind of containing the palladium complex of carborane ligand and its preparation and application between double phosphines |
| CN110483581B (en) * | 2019-08-09 | 2021-05-11 | 上海应用技术大学 | Palladium complex containing diphosphine m-carborane ligand and preparation and application thereof |
| CN111454296A (en) * | 2020-04-07 | 2020-07-28 | 上海应用技术大学 | Palladium complex containing m-carborane triazole ligand and preparation method and application thereof |
| CN111454296B (en) * | 2020-04-07 | 2023-04-28 | 上海应用技术大学 | Palladium complex containing meta-carborane triazole ligand and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109575087B (en) | 2020-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109575087A (en) | The sandwich complex of iridium of double-core half of the ligand containing diimine, preparation method and applications | |
| CN110117299B (en) | Rhodium complex containing ortho-carbon boron alkyl benzimidazole structure and preparation and application thereof | |
| CN107011145B (en) | Method for preparing 2-iodopent-2-ene-1, 4-dione derivative by visible light catalysis | |
| CN108620130A (en) | The o-C of carborane containing ortho position2B10H10The trivalent complex of iridium of structure, preparation method and applications | |
| CN110372755B (en) | N, N-coordinated palladium complex containing meta-carborane ligand, and preparation and application thereof | |
| CN110627841B (en) | Iron complex containing m-carborane triazole ligand and preparation and application thereof | |
| CN111961087B (en) | Semi-sandwich ruthenium complex containing ortho-position carborane-based benzothiazole, and preparation and application thereof | |
| CN107880079B (en) | Cyclic N-heterocyclic bis-carbene-palladium complex and preparation method and application thereof | |
| CN110105404A (en) | The ruthenium complex of the benzoxazoles structure of carborane radical containing ortho position and its preparation and application | |
| CN110283078A (en) | A kind of polysubstituted Isosorbide-5-Nitrae alkadiene compound and preparation method thereof | |
| CN109293706A (en) | The trivalent iridium imine composition of the dual key of nitrogen containing iridium, preparation method and applications | |
| CN109651445A (en) | A kind of preparation and its application of big steric hindrance trivalent rhodium imine composition | |
| CN110016061B (en) | Ruthenium complex containing carboranyl benzimidazole structure, preparation method and application thereof | |
| CN112375105A (en) | Nickel complex containing meta-carborane ligand and preparation method and application thereof | |
| CN109422700A (en) | A kind of synthetic method of N- acetyl group quinoxaline -2- amide and its derivative | |
| CN107915653B (en) | Method for preparing amide by catalyzing ester and amine to react | |
| CN112538096B (en) | Application of half-sandwich rhodium complex containing ortho-carboranyl benzoxazole structure | |
| Wang et al. | Synthesis, structure and electrochemistry of new diferrocenyl pyridine derivatives | |
| CN109867702B (en) | Binuclear palladium/ruthenium complex and preparation and application thereof | |
| CN113173859B (en) | Method for synthesizing chiral alpha-amino alcohol compound | |
| CN112871218B (en) | Neutral nickel complex containing ortho-carborane-based benzothiazole, and preparation and application thereof | |
| CN113004181B (en) | Method for preparing thioester compound by carbonylation | |
| CN110201720B (en) | Application of binuclear rhodium complex in fatty amine N-methylation reaction | |
| CN108383754B (en) | Preparation method and application of aryl oxime ester compound | |
| CN110368989B (en) | Application of palladium complex in fatty amine formylation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |