Amino alcohol nickel complex as well as preparation method and application thereof

Abstract

The invention discloses an amino alcohol nickel complex as well as a preparation method and application thereof, and belongs to the technical field of organic metal synthesis. The molecular formula of the amino alcohol nickel complex is Ni [OCR1R2 (CH2) mNR3R4] 2, comprising the following raw materials: a nickel-containing complex, 60wt.% of NaH and HOCR1R2 (CH2) mNR3R4, the preparation method specifically comprises the following steps: (1) under the protection of nitrogen, mixing a nickel-containing complex, 60wt.% NaH, HOCR1R2 (CH2) mNR3R4 and toluene, carrying out heating reaction, and carrying out heating reaction again; and (2) filtering, concentrating, cooling, filtering again, and washing to obtain the product. The nickel-containing complex, sodium hydride and amino alcohol are synthesized into the amino alcohol nickel complex through a one-pot method, the raw materials are simple, easy to obtain and convenient to store, expensive active intermediates do not need to be synthesized or purchased, and the cost and risk of amplified production are reduced. Meanwhile, the purification method of the product is improved, the high-purity amino alcohol nickel complex is obtained through a low-temperature crystallization method, operation is safe and convenient, the industrial purification efficiency is improved, and the purity of the obtained product is as high as 6N-7N through ICP-MS testing.

Description

Technical Field

[0001] This invention relates to the field of organometallic synthesis technology, and more specifically to an amino alcohol nickel complex, its preparation method, and its application. Background Technology

[0002] Nickel-containing precursors are widely used in semiconductor gates, hydrogen storage devices, and thin film deposition of nanomaterials. However, some known nickel-containing precursors, including nickel tetracarbonyl (Ni(CO)4), nickel dicenocene, nickel β-diketone carboxylate, and nickel β-diketone imide, suffer from drawbacks in safety and stability, hindering their widespread application. In contrast, nickel amino alcohol complexes exhibit good stability and volatility, representing a novel type of nickel-containing precursor that can form nickel films with improved quality under mild conditions.

[0003] Currently, there are two commonly used routes for synthesizing nickel amino alcohol complexes:

[0004] 1. Aminol nickel complexes are obtained by alcohol exchange between small molecule nickel alcohols such as nickel methoxide or nickel ethanol and amino alcohols.

[0005] The reaction equation is:

[0006] Ni(OY)2+2HOCR1R2(CH2)mNR3R4→Ni[OCR1R2(CH2)mNR3R4]2+2YOH;

[0007] Where X is a halogen, Y is a C1-C4 alkyl group, M is Li or Na, and R1, R2, R3, and R4 are linear or branched C1-C4 alkyl groups, and m = 1-3 (all positive integers).

[0008] However, this method requires the use of nickel alkoxide, which is rarely available domestically or internationally, and is expensive and difficult to obtain. Making nickel alkoxide in-house requires nickel chloride and the corresponding lithium alkoxide, a complicated process.

[0009] The reaction equation is:

[0010] NiCl2 + 2MOY → Ni(OY)2 + 2MCl.

[0011] 2. The amino alcohol nickel complex is obtained by reacting the sodium salt of the corresponding amino alcohol with nickel amine chloride under heating.

[0012] The reaction equation is:

[0013] 2MOCR1R2(CH2)mNR3R4+Ni(NH3)6Cl2→Ni[OCR1R2(CH2)mNR3R4]2+2MX+6NH3;

[0014] Where M is Li or Na, and R1, R2, R3, and R4 are linear or branched C1-C4 alkyl groups, m = 1-3.

[0015] However, this approach requires the use of sodium salts of alcoholamine ligands, which are difficult to store and transport, rarely available, expensive, and hard to obtain.

[0016] Existing invention patents all involve a cumbersome process of preparing intermediates through 2-3 steps before synthesizing amino alcohol nickel complexes. Furthermore, purifying high-purity amino alcohol nickel via distillation or sublimation requires high temperatures, which is inefficient for large-scale production. Moreover, the use of relatively clean nickel sources limits the availability of reaction raw materials.

[0017] Therefore, how to quickly and easily prepare an amino alcohol nickel complex is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0018] In view of this, the purpose of the present invention is to provide an amino alcohol nickel complex, its preparation method and application, so as to overcome the shortcomings of the prior art.

[0019] To achieve the above objectives, the present invention adopts the following technical solution:

[0020] An amino alcohol nickel complex with the molecular formula: Ni[OCR1R2(CH2] m NR3R4]2;

[0021] Wherein, R1, R2, R3, and R4 are linear or branched C1-C4 alkyl groups, and m = 1-3 (all positive integers).

[0022] The above-mentioned nickel-containing amino alcohol complex comprises the following raw materials: a nickel-containing complex, 60 wt.% sodium hydride (NaH), and amino alcohol HOCR1R2(CH2). m NR3R4, with a molar ratio of 1:(2~3):(2~3), preferably 1:2:2.05;

[0023] Wherein, R1, R2, R3, and R4 are linear or branched C1-C4 alkyl groups, and m = 1-3 (all positive integers).

[0024] Furthermore, the aforementioned nickel-containing complex is nickel hexaaminochloride (Ni(NH3)6Cl2), nickel hexaaminobromide (Ni(NH3)6Br2), or nickel hexaaminoiodide (Ni(NH3)6I2), preferably nickel hexaaminochloride.

[0025] The preparation method of the above-mentioned nickel amino alcohol complex specifically includes the following steps:

[0026] (1) Under nitrogen protection, a nickel-containing complex, 60 wt.% NaH, and HOCR1R2(CH2) were added. m NR3R4 was mixed with toluene (solvent) in a molar ratio of 1:(2~3):(2~3), and the mixture was heated to react. The mixture was heated again to react to obtain a reaction solution.

[0027] The reaction equation is:

[0028] Ni(NH3)6Cl2 + 60% NaH + HOCR1R2(CH2)mNR3R4→Ni[OCR1R2(CH2)mNR3R4]2+H2+NH3+NaCl;

[0029] Wherein, R1, R2, R3, and R4 are linear or branched C1-C4 alkyl groups, and m = 1-3 (all positive integers);

[0030] (2) The reaction solution was filtered, concentrated, cooled, filtered again, and washed to obtain the nickel amino alcohol complex.

[0031] Furthermore, in step (1) above, the nickel-containing complex is hexaaminonickel chloride, hexaaminonickel bromide, or hexaaminonickel iodide.

[0032] Furthermore, in step (1) above, the temperature of the heating reaction is 35-45℃ and the time is 4-8h.

[0033] Furthermore, in step (1) above, the temperature of the reaction is raised again to 70-100℃ and the time is 12-18h.

[0034] Furthermore, in step (2) above, the filtration is anhydrous and oxygen-free filtration.

[0035] Furthermore, in step (2) above, the cooling temperature is -30 to -20°C and the time is 12 to 24 hours.

[0036] Furthermore, in step (2) above, the temperature for the second filtration is -30 to -20°C.

[0037] Furthermore, in step (2) above, the washing reagent is cold toluene at -30 to -20°C, and the washing is performed three times.

[0038] The present invention also claims the use of the above-described nickel amino alcohol complex or the nickel amino alcohol complex prepared by the above-described preparation method in the thin film deposition of semiconductor gates, hydrogen storage devices, and nanomaterials.

[0039] As can be seen from the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows:

[0040] This invention improves the synthesis process by using a one-pot method to synthesize nickel amino alcohol complexes from nickel chloride, sodium hydride, and amino alcohols. The raw materials are simple, readily available, and easy to store, eliminating the need to synthesize or purchase expensive active intermediates, thus reducing the cost and risk of scale-up production. Furthermore, this invention improves the product purification method by obtaining high-purity nickel amino alcohol complexes through low-temperature crystallization. This method is safe and convenient, improves purification efficiency for industrial applications, and the obtained product achieves a purity of 6N–7N as determined by ICP-MS. Detailed Implementation

[0041] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0042] Example 1

[0043] The preparation method of the amino alcohol nickel complex (di(dimethylamino-2-methyl-2-propoxy)nickel(II), [Ni(dmamp)2]) specifically includes the following steps:

[0044] (1) The reaction flask was purged with nitrogen three times, and 1 mol Ni(NH3)6Cl2, 2 mol 60% wt. NaH, 2.05 mol HOC(CH3)2CH2N(CH3)2 and 2 L toluene were added and mixed. The mixture was heated to 35℃ and reacted for 5 h, and then heated to 80℃ and reacted for 12 h to obtain the reaction solution.

[0045] (2) The reaction solution was filtered through anhydrous and oxygen-free filter, concentrated to 400 mL, cooled to -20 °C for 12 h, filtered through a low temperature filtration device at -20 °C, and washed three times with 200 mL of -20 °C cold toluene to obtain the amino alcohol nickel complex.

[0046] Example 2

[0047] The preparation method of the amino alcohol nickel complex (di(diethylamino-2-methyl-2-propoxy)nickel(II), [Ni(deamp)2]) specifically includes the following steps:

[0048] (1) The reaction flask was purged with nitrogen three times, and 1 mol Ni(NH3)6Cl2, 2 mol 60% wt. NaH, 2.05 mol HOC(CH3)2CH2N(CH2CH3)2 and 2 L toluene were added and mixed. The mixture was heated to 45℃ and reacted for 8 h, and then heated to 90℃ and reacted for 24 h to obtain the reaction solution.

[0049] (2) The reaction solution was filtered through anhydrous and oxygen-free filter, concentrated to 400 mL, cooled to -30 °C for 12 h, filtered through a low temperature filtration device at -30 °C, and washed three times with 200 mL of -30 °C cold toluene to obtain the amino alcohol nickel complex.

[0050] Example 3

[0051] The preparation method of the amino alcohol nickel complex (di(dimethylamino-2-methyl-2-butoxy)nickel(II), [Ni(dmamb)2]) specifically includes the following steps:

[0052] (1) The reaction flask was purged with nitrogen three times, and 1 mol Ni(NH3)6Cl2, 2 mol 60% wt. NaH, 2.05 mol HOC(CH3)(CH2CH3)CH2N(CH3)2 and 2 L of toluene were added and mixed. The mixture was heated to 40℃ and reacted for 5 h, and then heated to 85℃ and reacted for 12 h to obtain the reaction solution.

[0053] (2) The reaction solution was filtered through anhydrous and oxygen-free filter, concentrated to 400 mL, cooled to -20 °C for 12 h, filtered through a low temperature filtration device at -20 °C, and washed three times with 200 mL of -20 °C cold toluene to obtain the amino alcohol nickel complex.

[0054] Comparative Example 1

[0055] The preparation method of the amino alcohol nickel complex (di(dimethylamino-2-methyl-2-propoxy)nickel(II), [Ni(dmamp)2]) specifically includes the following steps:

[0056] 3.50 g (15.10 mmol) of Ni(NH3)6Cl2 was suspended in 50 mL of toluene in a 125 mL Schlenk flask, and 4.62 g (33.20 mmol) of sodium dimethylamino-2-methyl-2-propoxy [Na(dmamp)] was slowly added. The mixed solution gradually turned dark brown. The dark brown mixture was refluxed under a nitrogen atmosphere for 8 hours and then filtered. The resulting filtrate was distilled under vacuum to remove the solvent. The resulting solid was then distilled at 10 °C. -2 Torr was purified by sublimation at 60°C under reduced pressure to give 3.20 g of the title compound as a dark brown solid.

[0057] Comparative Example 2

[0058] The preparation method of the amino alcohol nickel complex (di(diethylamino-2-methyl-2-propoxy)nickel(II), [Ni(deamp)2]) specifically includes the following steps:

[0059] 2.00 g (8.63 mmol) of Ni(NH3)6Cl2 was suspended in 50 mL of toluene in a 125 mL Schlenk flask, and 2.90 g (17.34 mmol) of sodium diethylamino-2-methyl-2-propoxy [Na(dmamp)] was slowly added. The mixed solution gradually turned dark brown. The dark brown mixture was refluxed under a nitrogen atmosphere for 8 hours and then filtered. The resulting filtrate was distilled under vacuum to remove the solvent. The resulting solid was then distilled at 10 °C. -2 Torr was purified by sublimation at 60°C under reduced pressure to give 1.85 g of the title compound as a dark brown solid.

[0060] Comparative Example 3

[0061] The preparation method of the amino alcohol nickel complex (di(dimethylamino-2-methyl-2-butoxy)nickel(II), [Ni(dmamb)2]) specifically includes the following steps:

[0062] 4.50 g (19.3 mmol) of Ni(NH3)6Cl2 was suspended in 50 mL of toluene in a 125 mL Schlenk flask, and 6.00 g (38.6 mmol) of sodium dimethylamino-2-methyl-2-butoxy[Na(dmamb)] was slowly added. The mixture gradually turned dark brown. The dark brown mixture was refluxed under a nitrogen atmosphere for 8 hours and then filtered. The resulting filtrate was distilled under vacuum to remove the solvent. The liquid residue was then distilled at 10 °C. -2 Torr was purified by sublimation at 80°C under reduced pressure to give 5.07 g of the title compound in the form of a green liquid.

[0063] Performance testing

[0064] The amino alcohol nickel complexes were prepared according to the methods of Examples 1-3 of the present invention and Examples 1-3 of the prior art CN 101189250 B (as comparative examples 1-3), respectively. The yields were calculated, and the NMR purity and ICP-MS purity were determined.

[0065] The results are shown in Table 1.

[0066] Table 1 Comparison of yield and purity of nickel amino alcohol complexes in Examples 1-3 and Comparative Examples 1-3

[0067]

[0068]

[0069] As shown in Table 1, the yields of Ni(dmamp)₂, Ni(deamp)₂, and Ni(dmamb)₂ prepared by crystallization in Examples 1-3 are close to those of the products obtained by sublimation in Comparative Examples 1-3. However, the NMR and ICP-MS metal purity of the products obtained in Comparative Examples 1-3 were not mentioned, while the NMR purity of the products obtained by crystallization in Examples 1-3 of this invention is greater than 99.5%, and the metal purity of ICP-MS is 6N to 7N, which can be directly used for Ni thin film deposition.

[0070] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An amino alcohol nickel complex, characterized in that, The molecular formula is: Ni[OCR1R2(CH2)] m NR3R4]2; Wherein, R1, R2, R3, and R4 are linear or branched C1-C4 alkyl groups, and m = 1-3.

2. The amino alcohol nickel complex according to claim 1, characterized in that, The raw materials include: a nickel-containing complex, 60 wt.% NaH, and HOCR1R2(CH2). m NR3R4, molar ratio 1:(2~3):(2~3); Wherein, R1, R2, R3, and R4 are linear or branched C1-C4 alkyl groups, and m = 1-3.

3. The amino alcohol nickel complex according to claim 2, characterized in that, The nickel-containing complex is hexaaminonickel chloride, hexaaminonickel bromide, or hexaaminonickel iodide.

4. A method for preparing the amino alcohol nickel complex as described in any one of claims 1-3, characterized in that, Specifically, the following steps are included: (1) Under nitrogen protection, a nickel-containing complex, 60 wt.% NaH, and HOCR1R2(CH2) were added. m NR3R4 was mixed with toluene in a molar ratio of 1:(2~3):(2~3), and the mixture was heated to react. The mixture was heated again to react to obtain a reaction solution. Wherein, R1, R2, R3, and R4 are linear or branched C1-C4 alkyl groups, and m = 1-3; (2) The reaction solution was filtered, concentrated, cooled, filtered again, and washed to obtain the nickel amino alcohol complex.

5. The method for preparing an amino alcohol nickel complex according to claim 4, characterized in that, In step (1), the nickel-containing complex is hexaaminonickel chloride, hexaaminonickel bromide, or hexaaminonickel iodide.

6. The method for preparing an amino alcohol nickel complex according to claim 4, characterized in that, In step (1), the temperature of the heating reaction is 35-45°C and the time is 4-8 hours.

7. The method for preparing an amino alcohol nickel complex according to claim 4, characterized in that, In step (1), the temperature of the reheating reaction is 70-100°C and the time is 12-18h.

8. The method for preparing an amino alcohol nickel complex according to claim 4, characterized in that, In step (2), the filtration is anhydrous and oxygen-free filtration; the cooling temperature is -30 to -20°C, and the time is 12 to 24 hours.

9. The method for preparing an amino alcohol nickel complex according to claim 4, characterized in that, In step (2), the temperature for the second filtration is -30 to -20°C; the washing reagent is cold toluene at -30 to -20°C, and the process is repeated three times.

10. The use of an amino alcohol nickel complex as described in any one of claims 1-3 or an amino alcohol nickel complex prepared by the preparation method as described in any one of claims 4-9 in thin film deposition of semiconductor gates, hydrogen storage devices, and nanomaterials.

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