Half-sandwich cyclometalated ruthenium coordination compound, and preparation method and application thereof

A technology of coordination compound and cyclometallization, applied in the field of synthetic chemistry, can solve the problems of high cost, high reaction pressure and high production cost, and achieve the effects of low cost, simple operation and little environmental pollution

Active Publication Date: 2015-12-16
ANHUI NORMAL UNIV
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Problems solved by technology

[0005] In view of the above-mentioned prior art, the purpose of the present invention is to overcome the most commonly used preparation method of aniline and its derivatives in the prior art is iron powder reduction method, because of its high requirements for equipment in the production process, pollutes the environment, consumes a lot of energy, and the product Disadvantages such as troublesome separation make it costly and pollute the environment in actual use; another preparation method is catalytic hydrogenation, the main disadvantage of this method is that the reaction requires high pressure, resulting in higher production costs, etc. problem, thereby providing a half-sandwich cyclometalated ruthenium coordination compound and its preparation method, and making it have low cost, simple operation, and less environmental pollution when it is applied to the preparation of aniline and its derivatives

Method used

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  • Half-sandwich cyclometalated ruthenium coordination compound, and preparation method and application thereof
  • Half-sandwich cyclometalated ruthenium coordination compound, and preparation method and application thereof
  • Half-sandwich cyclometalated ruthenium coordination compound, and preparation method and application thereof

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preparation example Construction

[0023] The present invention also provides a method for preparing the half-sandwich cyclometalated ruthenium complex described above, wherein the preparation method includes: under the condition of the presence of a protective gas, the compound shown in formula (B) The compound, dichloro(p-methylisopropylphenyl) ruthenium (II) dimer, base and solvent are mixed at a temperature of 80-110° C. for 15-20 hours to prepare a half-sandwich cyclometalated ruthenium complex compound;

[0024]

[0025] Among them, R 1 is Cl, Br or CH 3 .

[0026] Through the above technical scheme, the present invention reacts after mixing the compound shown in formula (B) and dichloro(p-methylisopropylphenyl) ruthenium (II) dimer, so that it can be synthesized in one step by a simple method A cyclometalated ruthenium complex with a semi-sandwich structure that exists stably in air.

[0027] Above-mentioned mixing method can be only simple mixing, and make it react in the mixing process, certainl...

Embodiment 1

[0046] Put 1 mmol of dichloro(p-methylisopropylphenyl) ruthenium (II) dimer, 2.4 mmol of L1 and 4 mmol of potassium acetate into a 50 mL reaction tube, and take 25 mL of acetonitrile as a solvent. The above mixture was heated, stirred and refluxed for 20 hours, then cooled to room temperature. The solvent was then removed using a rotary evaporator, and the resulting solid was washed with diethyl ether. The product was recrystallized from ethyl acetate and dichloromethane and dried to give 811 mg of the green product 1a in 87% yield. The parameters of the proton nuclear magnetic spectrum and the carbon nuclear magnetic spectrum of the product made are: 1 HNMR (500MHz, CDCl 3 ,ppm): δ=8.09(s,1H),7.26(d,1H),6.96(d,1H),5.54(d,1H),5.45(d,1H),5.22(d,1H),5.00(d ,1H),4.77-4.71(t,2H),4.19-4.12(t,2H),2.55(m,1H),2.06(s,3H),1.09(d,3H),1.00(d,3H). 13 CNMR (125MHz, CDCl 3 , ppm): δ=184.59, 174.07, 138.89, 136.79, 129.63, 127.50, 123.05, 101.93, 100.20, 88.20, 88.07, 82.63, 81.40, 71.19...

Embodiment 2

[0049] Put 1 mmol of dichloro(p-methylisopropylphenyl) ruthenium (II) dimer, 2.4 mmol of L2 and 4 mmol of potassium acetate into a 50 mL reaction tube, and take 25 mL of acetonitrile as a solvent. The above mixture was heated, stirred and refluxed for 20 hours, then cooled to room temperature. The solvent was then removed using a rotary evaporator, and the resulting solid was washed with diethyl ether. The product was recrystallized from ethyl acetate and dichloromethane and dried to give 869 mg of the green product 1b in 85% yield. The parameters of the proton nuclear magnetic spectrum and the carbon nuclear magnetic spectrum of the product made are: 1 HNMR (500MHz, CDCl 3 ,ppm): δ=8.26(s,1H),7.20(d,1H),7.12(d,1H),5.54(d,1H),5.46(d,1H),5.22(d,1H),4.50(d ,1H),4.77-4.69(t,2H),4.18-4.10(t,2H),2.55(m,1H),2.06(s,3H),1.09(d,3H),1.00(d,3H). 13 CNMR (500MHz, CDCl 3 , ppm): δ=185.15, 174.21, 141.62, 130.01, 127.79, 126.44, 125.85, 101.97, 100.25, 88.19, 88.08, 82.68, 81.34, 71.20...

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Abstract

The invention discloses a half-sandwich cyclometalated ruthenium coordination compound, and a preparation method and application thereof. The structure of the half-sandwich cyclometalated ruthenium coordination compound is shown as a formula (A), and R1 is Cl, Br or CH3. The preparation method comprises under the condition of existence of a protection gas, mixing a compound shown as a formula (B), dichloro(p-cymene)ruthenium(II) dimer, an alkaline and a solvent at a temperature of 80-110 DEG C for 15-20 h, so as to prepare the half-sandwich cyclometalated ruthenium coordination compound, and R1 is Cl, Br or CH3. According to the technical scheme, the compound shown as the formula (B) and dichloro(p-cymene)ruthenium(II) dimer are subjected to one-step reaction for preparing the half-sandwich cyclometalated ruthenium coordination compound, and the half-sandwich cyclometalated ruthenium coordination compound is applied to catalytically reduce nitrobenzene compounds for preparing aniline and derivatives thereof, so that the effects of low cost, simple operation and small environment pollution are realized.

Description

technical field [0001] The invention relates to the technical field of synthetic chemistry, in particular to a semi-sandwich cyclometalated ruthenium coordination compound and its preparation method and application. Background technique [0002] Ruthenium complexes with a semi-sandwich structure have unique chemical stability, excellent optical properties, and rich redox properties. field. At the same time, coordination compounds with semi-sandwich structure ruthenium play important applications in photochemistry, organic catalysis, olefin metathesis, electrochemistry, fluorescent ion probes, and gas sensing. In comparison, the semi-sandwich structure ruthenium complex has a novel structure, 1-methyl-4-isopropyltoluene as a planar molecule can shield half of the metal, on the one hand, it is beneficial to directional bonding; on the other hand, it can improve The solubility of the ruthenium complex is beneficial to realize its functional application. Therefore, it is very...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00B01J31/22C07C211/51C07C211/46C07C211/47C07C209/36
Inventor 贾卫国张台
Owner ANHUI NORMAL UNIV
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