Preparation and application of carborane benzothiazole ligand containing semi-sandwich iridium complex

A technology of benzothiazole and iridium complexes, applied in the field of semi-sandwich iridium complexes and their preparation, can solve the problems of poor stability, harsh preparation and storage conditions, etc., and achieve high stability, excellent selectivity, stable physical and chemical properties Effect

Active Publication Date: 2019-05-21
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In addition, most of the catalysts for olefin polymerization, especially ethylene polymerization, are early transition metal compounds. The stability of these compounds is very poor, and the preparation and storage conditions are usually quite harsh.

Method used

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  • Preparation and application of carborane benzothiazole ligand containing semi-sandwich iridium complex
  • Preparation and application of carborane benzothiazole ligand containing semi-sandwich iridium complex
  • Preparation and application of carborane benzothiazole ligand containing semi-sandwich iridium complex

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Example 1: Synthesis of half-sandwich iridium complexes containing carborane benzothiazole ligands

[0025]

[0026] At –78°C, n-BuLi (1.6M) n-hexane solution (1.00mL, 1.6mmol) was slowly added dropwise to the ortho carborane o-C 2 B 10 h 10 (92.0mg, 0.64mmol) in tetrahydrofuran solution, continue stirring at this temperature for 30 minutes after the dropwise addition, slowly rise to room temperature and continue the reaction for 1 hour, then add bromobenzothiazole (137.0mg, 0.64mmol), continue The reaction was carried out at room temperature for 6 hours. Then the binuclear iridium compound [Cp*IrCl 2 ] 2 (256.0 mg, 0.32 mmol) was added to the reaction system for another 3 hours. After the reaction is finished, stand and filter, and dry the solvent under reduced pressure, and the obtained crude product is subjected to column chromatography separation (petroleum ether / tetrahydrofuran=6:1) to obtain the red target product, the carborane shown in formula (I) Half-...

Embodiment 2

[0029] Embodiment 2: catalytic ethylene polymerization reaction

[0030] The semi-sandwich iridium complex (i.e. catalyst Ir) containing the carborane benzothiazole ligand shown in the formula (I) prepared in Example 1 is used to catalyze ethylene polymerization: under anhydrous and oxygen-free conditions, in a reaction vessel Add 1mL of half-sandwich iridium catalyst in chlorobenzene solution (0.1 μmol), MAO in toluene solution 0.19mL (300 μmol), the ratio of the amount of semi-sandwich iridium complex to MAO is 1:3000, and ethylene gas is introduced at normal pressure , the gas flow rate is 6mL / s, the ethylene polymerization reaction is carried out under anhydrous and oxygen-free conditions, the reaction temperature is 30 ° C, after 15 minutes of reaction, the reaction is terminated with an ethanol solution containing 10% hydrochloric acid by volume, and the resulting product is filtered and used Wash with ethanol several times, and dry in vacuum at 60-80°C until the quality...

Embodiment 3

[0031] Embodiment 3: catalytic ethylene polymerization reaction

[0032] The semi-sandwich iridium complex (i.e. catalyst Ir) containing the carborane benzothiazole ligand shown in the formula (I) prepared in Example 1 is used to catalyze ethylene polymerization: under anhydrous and oxygen-free conditions, in a reaction vessel Add the chlorobenzene solution (0.5 μ mol) of 5mL semi-sandwich iridium catalyst successively, the toluene solution 0.32mL (500 μ mol) of MAO, the ratio of the amount of substance of catalyst Ir and MAO is 1:1000, and normal pressure feeds ethylene gas, gas flow rate 6mL / s, carry out ethylene polymerization reaction under anhydrous and oxygen-free conditions, the reaction temperature is 30 ℃, after 15 minutes of reaction, stop the reaction with ethanol solution containing 10% hydrochloric acid by volume, filter the obtained product, and wash several times with ethanol The second time, vacuum-dry at 60-80°C until the quality remains unchanged. The activi...

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Abstract

The invention provides an ortho-carborane based benzothiazole structure containing semi-sandwich iridium complex and a preparation method thereof. According to the ortho-carborane based benzothiazolestructure containing semi-sandwich iridium complex, a dinuclear iridium compound [Cp*IrCl2]2 is used as a raw material, and the dinuclear iridium compound reacts with n-BuLi and ortho-carborane basedbenzothiazole to obtain a trivalent iridium complex with the ortho-carborane based benzothiazole structure. A synthetic process provided by the invention is simple and environment-friendly, and has excellent selectivity and higher yield. The ortho-carborane based benzothiazole structure containing semi-sandwich iridium complex provided by the invention has stable physicochemical property, thermalstability and the like, the polymerization of ethylene can be efficiently catalyzed at an atmospheric pressure under a condition with MAO as a catalyst promoter, and the obtained polymer also has higher molecular weight.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry, and in particular relates to a semi-sandwich iridium complex containing an ortho carboryl benzothiazole structure and a preparation method and application thereof. Background technique [0002] Carborane-based metal complexes are widely used as catalysts in the chemical industry, and in such compounds, semi-sandwich structure organometallic complexes have a more novel structure, and their structure has the following advantages: (1) cyclopentadiene The alkenyl group shields half of the metal, which is beneficial to directional bond formation; (2) By changing the substituent of the cyclopentadienyl group, the solubility of the metal complex can be improved, which is beneficial to realize its functional application. Therefore, it is of great significance to explore the metal-organic compounds with semi-sandwich structure and their synthesis methods based on carboranes as ligands. In add...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F17/02C08F110/02C08F4/70
Inventor 姚子健靳永旭云雪静高永红邓维
Owner SHANGHAI INST OF TECH
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