CN104230999A - Method for preparing dicarbonyl iridium acetylacetonate (I) - Google Patents
Method for preparing dicarbonyl iridium acetylacetonate (I) Download PDFInfo
- Publication number
- CN104230999A CN104230999A CN201410412042.6A CN201410412042A CN104230999A CN 104230999 A CN104230999 A CN 104230999A CN 201410412042 A CN201410412042 A CN 201410412042A CN 104230999 A CN104230999 A CN 104230999A
- Authority
- CN
- China
- Prior art keywords
- iridium
- acac
- methyl ethyl
- cyclooctadiene
- reacting
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing dicarbonyl iridium acetylacetonate (I). Dicarbonyl iridium acetylacetonate (I) is a precursor compound for preparing an iridium coating by MOCVD (metal-organic chemical vapor deposition), and is also a common carbonyl addition homogeneous catalyst. The method mainly comprises the following steps: (1) reacting iridous chloride hydrate and 1,5-cyclooctadiene to generate an intermediate (1,5-cyclooctadiene) iridium chloride (I) dimer; and (2) reacting the intermediate and carbon monoxide to introduce carbonyl group, reacting with acetylacetone to obtain the dicarbonyl iridium acetylacetonate (I). The preparation method has the advantages of simple technical process, high yield and high product purity, and is suitable for mass preparation of [Ir(CO)2(acac)].
Description
Technical field
The present invention relates to a kind of preparation method of metal organo-iridium compounds methyl ethyl diketone dicarbapentaborane iridium (I), belong to chemical field.
Background technology
Metal organic chemical vapor deposition (MOCVD) method prepares the common method of iridium coating material, and the key of the method selects suitable precursor compound according to the characteristic of matrix and mode of deposition.Meet MOCVD and require organometallics, be generally the characteristic should at a lower temperature with volatilization, distillation, metal or its oxide compound can be decomposited at a higher temperature simultaneously.At present, applying maximum compounds is beta-diketon metal compound, as methyl ethyl diketone iridium (III).But methyl ethyl diketone iridium (III) sublimation temperature Sum decomposition temperature is higher, and carbon content is high, has produced carbon codeposition phenomenon.[Ir (CO)
2(acac)] structural formula is as follows, and as the organometallics of monovalence iridium, sublimation temperature Sum decomposition temperature is all lower, not easily produces the codeposition of carbon, is therefore also a kind of comparatively ideal MOCVD presoma.Meanwhile, [Ir (CO)
2(acac)] due to can activated carbonyl, be also a kind of important Carbonyl addition homogeneous catalyst, can be used for ethanol low pressure carbonylation synthesis of acetic acid.At present, due to the relative low price of iridium, at some factories [Ir (CO)
2(acac)] part instead of the carbonylating catalyst of rhodium, is applied in actual production,
[Ir (CO)
2(acac) structural formula].
[Ir (CO)
2(acac) difficulty of preparation technology] is large, productive rate is low, and current document openly reports that preparation technology mainly contains three kinds of [F.Bonati, R.Ugo.J.Organometal.Chem.1968,11:341-352.; N.B.Morozova, P.P.Semyannikov, S.V.Trubin, P.P.Stabnikov, A.A.Bessonov, K.V.Zherikova, I.K.Igumenov.J.Therm.Anal.Calorim.2009,91 (1): 261-266.; D.Roberto, E.Cariati, R.Psaro, R.Ugo.Organometallics.1994,13 (11): 4227-4231.], relate to three routes:
Route 1
Ir(CO)
2(NH
2CH(CH
3)
3(μ-Cl)+C
5H
8O
2→[Ir(CO)
2(acac)]+[C
3H
7NH
3]Cl
Route 2
Route 3
Above-mentioned is the synthetic route of methyl ethyl diketone dicarbapentaborane iridium (I).
Wherein, route 1 is with Ir (CO)
2(NH
2cH (CH
3)
3(μ-Cl) is starting raw material, although a step can prepare [Ir (CO)
2], but Ir (CO) (acac)
2(NH
2cH (CH
3)
3(μ-Cl) synthesis itself is very difficult, expensive, and preparation cost is high.
Route 2 is raw material with chloro-iridic acid, prepares (1,5-cyclooctadiene) iridium chloride (I) [Ir (COD) (μ-Cl)]
2after, introduce methyl ethyl diketone and obtain methyl ethyl diketone two (1,5-cyclooctadiene) iridium (I) [Ir (COD)
2(acac)], last carbonylate obtains [Ir (CO)
2(acac)], productive rate only can reach 75%.
Route 3 is with bicyclooctene iridium chloride (I) [Ir (COT)
2(μ-Cl)]
2for raw material, experience [Ir (CO)
2(μ-Cl)]
2intermediate, not only productive rate only has 50%, but also will synthesize [Ir (COT) in advance
2(μ-Cl)]
2raw material, productive rate is only 59%.
These three routes all exist that to prepare productive rate low, and the problem that cost is high, therefore, necessary development is suitable for mass preparation [Ir (CO)
2(acac) efficient synthetic technology].
Summary of the invention
We are by the optimization of above three syntheti c routes and improvement, invent a kind of new syntheti c route, namely with basic compound hydrated iridium trichloride for raw material, first with 1,5-cyclooctadiene (COD) reacts, and prepares intermediate [Ir (COD) (μ-Cl)]
2dimer, intermediate and reaction of carbon monoxide carbonylate, then [Ir (CO) is obtained by reacting with methyl ethyl diketone
2(acac)].
Syntheti c route is as follows:
Feature of the present invention adopts the hydrated iridium trichloride of easily acquisition and 1,5-cyclooctadiene to react a step to obtain intermediate [Ir (COD) (μ-Cl)]
2, this reaction times is short, productive rate high (> 95%); Intermediate and reaction of carbon monoxide carbonylate, be obtained by reacting [Ir (CO) with methyl ethyl diketone
2(acac)], this productive rate prepared is greater than 90%, product purity >99%.
Embodiment
Embodiment 1: by IrCl
33H
2o (2.0g, 2.84mmol) and 30mL secondary deionized water, 80mL ethanol and 20mL1,5-cyclooctadiene are placed in the round-bottomed flask of 250mL, under standard Schlenk vacuum line technical controlling, and stirring heating back flow reaction 5h.Stopped reaction, concentration of reaction solution, removes most of solvent, and solid is separated out, and filters, filter cake distilled water, methanol wash.Vacuum-drying 5h, obtains 1.81g, and productive rate is 95.2%.
By [Ir (COD) (μ-Cl)]
2(1.0g, 1.49mmol) and 150mL tetrahydrofuran (THF) (THF) are placed in the round-bottomed flask of 250mL, under standard Schlenk vacuum line technical controlling, under system is in argon atmosphere.Then pass into CO gas 3min, solution is become black-and-blue from yellow.Under argon atmosphere, add NaHCO rapidly
3(10g, 119.04mmol) and 1.5mL methyl ethyl diketone (Hacac).Stirring heating 70 DEG C reaction 3h, solution becomes yellow again.Stopped reaction, cooling, filter, concentrated filtrate, removes most of solvent, and solid is separated out, and filters, filter cake distilled water wash three times.Vacuum-drying 5h, obtains 0.93g, and productive rate is 90.3%.
Feature structure parameter: (1) ultimate analysis: theoretical value C24.4%, H2.0% and theoretical value C24.2%, H2.0% consistent; (2) mass spectrum (EI): m/z theoretical value: 347, measured value: 347; (3) proton nmr spectra (
1hNMR, CDCl
3): at δ (ppm) 5.78 (s, 1H, C
γ-H, acac), 2.10 (s, 6H, CH
3, acac); (4) ultra-red mass spectrum IR (cm
-1, KBr) and 2046 (s, ν (CO)), 1996 (s); (5) be [Ir (CO) below
2(acac) crystalline structure].These parameters meet the chemical structure of methyl ethyl diketone dicarbapentaborane iridium (I) compound.
[Ir (CO)
2(acac) molecular structure].
Embodiment 2: by IrCl
33H
2o (10.0g, 14.2mmol) and 150mL secondary deionized water, 400mL ethanol and 100mL1,5-cyclooctadiene are placed in the round-bottomed flask of 1000mL, under standard Schlenk vacuum line technical controlling, and stirring heating back flow reaction 5h.Stopped reaction, concentration of reaction solution, removes most of solvent, and solid is separated out, and filters, filter cake distilled water, methanol wash.Vacuum-drying 5h, obtains 9.1g, and productive rate is 95.8%.
By [Ir (COD) (μ-Cl)]
2(5.0g, 7.45mmol) and 750mL tetrahydrofuran (THF) (THF) are placed in the round-bottomed flask of 1000mL, under standard Schlenk vacuum line technical controlling, under system is in argon atmosphere.Then pass into CO gas 3min, solution is become black-and-blue from yellow.Under argon atmosphere, add NaHCO rapidly
3(50g, 595.2mmol) and 7.5mL methyl ethyl diketone (Hacac).Stirring heating 70 DEG C reaction 3h, solution becomes yellow again.Stopped reaction, cooling, filter, concentrated filtrate, removes most of solvent, and solid is separated out, and filters, filter cake distilled water wash three times.Vacuum-drying 5h, obtains 4.68g, and productive rate is 90.9%.
Feature structure parameter: (1) ultimate analysis: theoretical value C24.4%, H2.0% and theoretical value C24.3%, H2.0% consistent; (2) mass spectrum (EI): m/z theoretical value: 347, measured value: 347; (3) proton nmr spectra (
1hNMR, CDCl
3): at δ (ppm) 5.78 (s, 1H, C
γ-H, acac), 2.10 (s, 6H, CH
3, acac); (4) ultra-red mass spectrum IR (cm
-1, KBr) and 2046 (s, ν (CO)), 1996 (s).
Embodiment 3: by IrCl
33H
2o (20.0g, 28.4mmol) and 300mL secondary deionized water, 800mL ethanol and 200mL1,5-cyclooctadiene are placed in the round-bottomed flask of 2000mL, under standard Schlenk vacuum line technical controlling, and stirring heating back flow reaction 5h.Stopped reaction, concentration of reaction solution, removes most of solvent, and solid is separated out, and filters, filter cake distilled water, methanol wash.Vacuum-drying 5h, obtains 18.2g, and productive rate is 95.8%.
By [Ir (COD) (μ-Cl)]
2(15.0g, 22.35mmol) and 2250mL tetrahydrofuran (THF) (THF) are placed in the round-bottomed flask of 3000mL, under standard Schlenk vacuum line technical controlling, under system is in argon atmosphere.Then pass into CO gas 3min, solution is become black-and-blue from yellow.Under argon atmosphere, add NaHCO rapidly
3(150g, 1785.6mmol) and 22.5mL methyl ethyl diketone (Hacac).Stirring heating 70 DEG C reaction 3h, solution becomes yellow again.Stopped reaction, cooling, filter, concentrated filtrate, removes most of solvent, and solid is separated out, and filters, filter cake distilled water wash three times.Vacuum-drying 5h, obtains 14.0g, and productive rate is 90.3%.
Feature structure parameter: (1) ultimate analysis: theoretical value C24.4%, H2.0% and theoretical value C24.3%, H2.0% consistent; (2) mass spectrum (EI): m/z theoretical value: 347, measured value: 347; (3) proton nmr spectra (
1hNMR, CDCl
3): at δ (ppm) 5.78 (s, 1H, C
γ-H, acac), 2.10 (s, 6H, CH
3, acac); (4) ultra-red mass spectrum IR (cm
-1, KBr) and 2046 (s, ν (CO)), 1996 (s).
As can be seen from embodiment, [Ir (CO)
2(acac) productive rate] can reach 86%, and method is suitable for batch preparation; The structural parameter of different batches meet [Ir (CO)
2(acac) chemical structure], and with document (K.V.Zheriktova, N.V.Kuratieva, N.B.Morozova.J.Struct.Chem.2009,50 (3): 574-576.) report consistent.
Claims (3)
1. prepare a method for methyl ethyl diketone dicarbapentaborane iridium (I), it is characterized in that have employed syntheti c route as follows:
Wherein: COD=1,5-cyclooctadiene, μ-Cl=chlorine abutment, Hacac=methyl ethyl diketone.
2. one according to claim 1 prepares the method for methyl ethyl diketone dicarbapentaborane iridium (I), it is characterized in that: described first latter two intermediate is [Ir (COD) (μ-Cl)] respectively
2dimer and [Ir (CO)
2(μ-Cl)]
2dimer.
3. one prepares the method for methyl ethyl diketone dicarbapentaborane iridium (I) according to claim 1, it is characterized in that: [Ir (COD) (μ-Cl)]
2be 1:10 with Hacac material molar ratio, temperature of reaction is 70 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410412042.6A CN104230999A (en) | 2014-08-20 | 2014-08-20 | Method for preparing dicarbonyl iridium acetylacetonate (I) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410412042.6A CN104230999A (en) | 2014-08-20 | 2014-08-20 | Method for preparing dicarbonyl iridium acetylacetonate (I) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104230999A true CN104230999A (en) | 2014-12-24 |
Family
ID=52219989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410412042.6A Pending CN104230999A (en) | 2014-08-20 | 2014-08-20 | Method for preparing dicarbonyl iridium acetylacetonate (I) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104230999A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078771A (en) * | 2019-06-06 | 2019-08-02 | 江苏欣诺科催化剂有限公司 | A kind of preparation method of iridium catalyst |
| CN115043883A (en) * | 2022-05-25 | 2022-09-13 | 昆明贵金属研究所 | Preparation method of acetylacetonatodicarbonyl iridium (I) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010020107A1 (en) * | 2000-01-10 | 2001-09-06 | Richard Walter | Method for producing [IrcodC1]2 |
| JP2006045089A (en) * | 2004-08-02 | 2006-02-16 | Daicel Chem Ind Ltd | METHOD FOR PRODUCING DI-mu-CHLOROBIS(1,5-CYCLOOCTADIENE) DIIRIDIUM(I) |
| CN102030781A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Preparation method for acetylacetonatodicarbonyl rhodium |
-
2014
- 2014-08-20 CN CN201410412042.6A patent/CN104230999A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010020107A1 (en) * | 2000-01-10 | 2001-09-06 | Richard Walter | Method for producing [IrcodC1]2 |
| JP2006045089A (en) * | 2004-08-02 | 2006-02-16 | Daicel Chem Ind Ltd | METHOD FOR PRODUCING DI-mu-CHLOROBIS(1,5-CYCLOOCTADIENE) DIIRIDIUM(I) |
| CN102030781A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Preparation method for acetylacetonatodicarbonyl rhodium |
Non-Patent Citations (3)
| Title |
|---|
| DOMINIQUE ROBERTO等，: "Formation of [Ir(CO)2¬Cl]X, (x = 2, n) Species by Mild Carbonylation of [Ir(cyclooctene)Cl]2 Supported on Silica or in Solution: A New Convenient Material for the Synthesis of Iridium(1) Carbonyl Complexes", 《ORGANOMETALLICS》 * |
| DOMINIQUE ROBERTO等，: "Formation of [Ir(CO)2¬Cl]X, (x = 2, n) Species by Mild Carbonylation of [Ir(cyclooctene)Cl]2 Supported on Silica or in Solution: A New Convenient Material for the Synthesis of Iridium(1) Carbonyl Complexes", 《ORGANOMETALLICS》, vol. 13, no. 11, 31 December 1994 (1994-12-31) * |
| N. B. MOROZOVA等，: "VAPOR PRESSURE OF SOME VOLATILE IRIDIUM(I) COMPOUNDS WITH CARBONYL, ACETYLACETONATE AND CYCLOPENTADIENYL LIGANDS", 《JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY》, vol. 96, 31 December 2009 (2009-12-31) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078771A (en) * | 2019-06-06 | 2019-08-02 | 江苏欣诺科催化剂有限公司 | A kind of preparation method of iridium catalyst |
| CN110078771B (en) * | 2019-06-06 | 2022-04-05 | 江苏欣诺科催化剂有限公司 | Preparation method of iridium catalyst |
| CN115043883A (en) * | 2022-05-25 | 2022-09-13 | 昆明贵金属研究所 | Preparation method of acetylacetonatodicarbonyl iridium (I) |
| CN115043883B (en) * | 2022-05-25 | 2024-05-07 | 昆明贵金属研究所 | Preparation method of iridium (I) acetylacetonate dicarbonyl |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102066251B (en) | Process for preparing higher hydridosilanes | |
| Tanaka et al. | Multi-electron reduction of CO2 via Ru CO2, C (O) OH, CO, CHO, and CH2OH species | |
| US10124321B2 (en) | Carbon nitride heterogeneous catalyst containing rhodium, method for preparing the same, and method for preparing acetic acid using the same | |
| CN101675020B (en) | Method for synthesizing optically active carbonyl compounds | |
| CN107602357B (en) | Method for preparing menthone | |
| Tanabe et al. | Preparation and reactivity of molybdenum–dinitrogen complexes bearing an arsenic-containing ANA-type pincer ligand | |
| CN113492021A (en) | Preparation method of rhodium catalyst | |
| CN104230999A (en) | Method for preparing dicarbonyl iridium acetylacetonate (I) | |
| US9061960B2 (en) | Method for working up mixtures | |
| CN112979703A (en) | Hydroformylation reaction ligand, hydroformylation catalyst and preparation method of dihydric alcohol | |
| WO2020161175A1 (en) | Process for the production of acetals from carbon dioxide | |
| KR860000448B1 (en) | Process for preparing alkanols from synthesis gas | |
| US9163045B2 (en) | Process for preparing diketonato-rhodium(I)-carbonyl complexes | |
| Wilklow-Marnell et al. | A POCO type pincer complex of iridium: Synthesis, characterization, and catalysis | |
| CN107986943B (en) | Synthesis method of cyclohexanedimethanol, catalyst and application thereof | |
| CN114560761A (en) | Method for synthesizing 2, 3-disubstituted indanone derivative in aqueous phase at one time | |
| CN110330421B (en) | Method for preparing tricyclodecanedicarboxylic acid by taking dicyclopentadiene as raw material | |
| CN115043883B (en) | Preparation method of iridium (I) acetylacetonate dicarbonyl | |
| Ardizzoia et al. | Oligomerization and polymerization of alkynes catalyzed by rhodium (I) pyrazolate complexes | |
| CN117884186B (en) | Catalyst for preparing optically active citronellal, and preparation method and application thereof | |
| CN110078771B (en) | Preparation method of iridium catalyst | |
| JPH06199730A (en) | Production of hydroxybutyraldehyde compound | |
| CN114437133A (en) | Iridium-containing complex and preparation method thereof | |
| CN114437132A (en) | Iridium phosphine complex and preparation method thereof | |
| RU2342390C1 (en) | METHOD OF OBTAINING 1,2,3,3a,4,5,6,7,8,9-DECAHYDROCYCLONONE[b]-MAGNESACYCLOPENTANE |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141224 |