Process and apparatus system for the preparation of dialkylamino metal halides, imido tris(dialkylamino) metal complexes

Abstract

The application relates to a preparation method and device system of a dialkylamino metal halide and an imino tri(dialkylamino) metal complex, the device system is matched with the preparation method, the preparation method provided by the application promotes the reaction of the generation of a favorable product by adjusting and controlling reaction conditions, reduces the occurrence of a side reaction, avoids the defects of introducing metal impurities by using n-butyl lithium, avoids the generation of lithium salt and other components inconvenient for subsequent separation, and facilitates the purification of a product; moreover, the dialkylamino metal halide and the imino tri(dialkylamino) metal complex prepared by the application meet the purity requirements of a precursor material in integrated circuit manufacturing.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor precursor material production technology, and relates to a method and apparatus system for preparing precursor materials, particularly to a method and apparatus system for preparing dialkylamino metal halides and iminotris(dialkylamino) metal complexes. Background Technology

[0002] Compounds of Group 5 elements have the characteristics of low resistivity, high melting point, high activation energy for lattice and grain boundary diffusion, and good thermal stability. Therefore, they are widely used in the integrated circuit manufacturing process.

[0003] Taking tantalum nitride as an example, tantalum nitride exhibits good high-temperature chemical stability with high-dielectric-constant dielectrics and is used as a metal gate material in CMOS processes below 45nm. Ta2O5 thin films have high dielectric constants and good chemical stability, and are used as high-dielectric-constant materials in decoupling filters to replace traditional SiO2 materials. This allows for greater capacitance density at the same physical thickness, effectively reducing leakage current density and improving device reliability and lifespan.

[0004] Copper has replaced aluminum for interconnects due to its superior conductivity, but copper requires a barrier layer to prevent its diffusion into the underlying structure. This barrier layer must be highly uniform, ultrathin, and conformal, taking into account the complex interconnect architecture. Atomic layer deposition (ALD) is one of the most efficient methods to meet these requirements due to the self-limiting reaction between the reactants and the substrate.

[0005] Group 5 transition metals include tantalum and niobium. Taking tantalum as an example, there are penta(dimethylamino)tantalum (Ta(NMe2)5), penta(diethylamino)tantalum (Ta(NEt2)5), and iminotris(dimethylamino)tantalum (R). 3 N=Ta(NMe2)3) is a very attractive tantalum-containing organometallic precursor material for tantalum nitride film deposition.

[0006] Ta(NR) of penta(dialkylamino)tantalum 1 R 2 The synthesis of 5 often employs dialkylamino lithium (LiNR) 1 R 2 Preparation process using tantalum halide (TaX5) as raw material:

[0007] TaX5+LiNR 1 R 2 →Ta(NR 1 R 2 )5+LiX

[0008] Taking penta(dimethylamino)tantalum Ta(NMe2)5 as an example, although this method can yield Ta(NMe2)5 in approximately 73% yield, it results in a mixture of unreacted TaCl5 and LiNMe2. This mixture can explode or undergo a highly exothermic reaction during separation, increasing the safety risks of the process. Furthermore, this reaction inevitably uses n-butyllithium, and the reaction conditions are relatively harsh. The use of such metal reagents easily introduces difficult-to-separate metallic impurities, affecting the purity of the final product; and the solid waste such as lithium halides generated during the reaction further increases the difficulty of separation.

[0009] Taking tantalum as an example, iminotris(dialkylamino)tantalum R 3 N = Ta(NR) 1 R 2 The synthesis methods for 3 include the following two approaches:

[0010] The first method is to first use LiNR. 1 R 2 The intermediate product penta(dialkylamino)tantalum Ta(NR) was prepared with Tax5. 1 R 2 )5, then with primary amine R 3 NH2 ligand exchange preparation of R 3 N = Ta(NR) 1 R 2 3:

[0011] TaX5+LiNR 1 R 2 →Ta(NR 1 R 2 )5+LiX

[0012] Ta(NR 1 R 2 )5+R 3 NH2→R 3 N = Ta(NR) 1 R 2 )3+HNR 1 R 2

[0013] The second method involves using Tax5 with 4 times the molar amount of LiNR. 1 R 2 1 molar amount of LiNHR 3 One-pot reaction to prepare R 3 N = Ta(NR) 1 R 2 3:

[0014] TaX5+4LiNR 1 R 2 +LiNHR3→R3 N = Ta(NR) 1 R 2 )3+5LiX+HNR 1 R 2

[0015] In the first method, primary amine R 3 NH2 and Ta(NR) 1 R 2 The ligand exchange reaction between TaX5 and LiNR is more suitable for aromatic primary amines than for aliphatic primary amines. The "one-pot" reaction in the second method is simple to operate, but involves TaX5 and LiNR. 1 R 2 LiNHR 3 The solid-phase reaction of amino lithium salts generally has a low yield, such as in the preparation of... t The overall yield of BuN=Ta(NMe2)3 is only 40%.

[0016] Moreover, both methods inevitably use n-butyllithium, which requires relatively harsh conditions and easily introduces difficult-to-separate metal impurities, affecting the purity of the final product; the solid waste such as lithium halides generated during the reaction process increases the difficulty of separation.

[0017] Therefore, in order to meet the purity requirements of precursor materials in the integrated circuit manufacturing process, it is necessary to develop a method and apparatus system for preparing dialkylamino metal halides and iminotris(dialkylamino) metal complexes that is easy to control, simple to separate, convenient to operate, and suitable for industrial production. Summary of the Invention

[0018] The purpose of this invention is to provide a method and apparatus system for preparing dialkylamino metal halides and iminotris(dialkylamino) metal complexes. The preparation method and apparatus system correspond to each other. This preparation method reduces the occurrence of side reactions, avoids metal impurity defects caused by the use of n-butyllithium, avoids the generation of lithium salts and other components that are not easy to separate in subsequent processes, and facilitates product purification. In addition, the dialkylamino metal halides and iminotris(dialkylamino) metal complexes obtained by this invention meet the purity requirements of precursors for integrated circuit manufacturing.

[0019] To achieve this objective, the present invention adopts the following technical solution:

[0020] In a first aspect, the present invention provides a method for preparing a dialkylamino metal halide, the method comprising the following steps:

[0021] Under protective atmosphere conditions and in an inert solvent, halide MX5 reacts with trimethylsilyldialkylamine Me3SiNR 1 R 2The reaction yields a dialkylamino metal halide solution, and the reaction proceeds as follows:

[0022] MX5+Me3SiNR 1 R 2 →M(NR 1 R 2 ) 5-n X n +Me3SiX;

[0023] M is a fifth subgroup element;

[0024] X is a halogen;

[0025] The value of n ranges from 0 to 1;

[0026] The R 1 With R 2 Each is independently an alkyl group, where N is an amino nitrogen and Me is a methyl group.

[0027] In the preparation method provided by this invention, the value of n ranges from 0 to 1. When the value of n is 0, the halide MX5 reacts with the trimethylsilyldialkylamine Me3SiNR. 1 R 2 The reaction yields a penta(dialkylamino) metal complex; when n is 1, the halide MX5 reacts with the trimethylsilyldialkylamine Me3SiNR. 1 R 2 The reaction yields a tetra(dialkylamino) halide.

[0028] In the method for preparing dialkylamino metal halides provided by this invention, trimethylsilyl dialkylamine Me3SiNR 1 R 2 As a reactant, it provides a dialkylamino ligand and also acts as a dehalogenating agent for the halide MX5. The dehalogenated product Me3SiX escapes in gaseous form during the reaction, which favors the forward reaction. Therefore, the boiling point of Me3SiX is particularly important for promoting the forward reaction. Based on the formation rate of Me3SiX, to advance the reaction forward, trimethylsilyldialkylamine Me3SiNR... 1 R 2 It can be added in batches or by dripping.

[0029] In this invention, M is a fifth subgroup element, including tantalum or niobium.

[0030] Preferably, the preparation method further includes a purification step of the obtained dialkylamino metal halide solution.

[0031] For example, the melting and boiling points of trimethylsilyl halides are as follows: Me3SiF has a melting point of -74°C and a boiling point of 16°C; Me3SiCl has a melting point of -40°C and a boiling point of 57°C; Me3SiBr has a melting point of -43°C and a boiling point of 79°C; and Me3SiI has a melting point <0°C and a boiling point of 106°C. When the byproduct Me3SiX escapes in gaseous form during the reaction, the trimethylsilyldialkylamine reactant, which serves as a dehalogenating agent, preferably remains in the system to continue the reaction. Therefore, trimethylsilyldialkylamine Me3SiNR is preferred. 1 R 2 Its boiling point is higher than that of the byproduct trimethylsilyl halide.

[0032] For example, when trimethylsilyldialkylamine Me3SiNR 1 R 2 When the reaction is Me3SiNMe2 (boiling point 84℃), the boiling point of the released trimethylsilyl halide is below 84℃, which favors the forward reaction. In this case, the preferred halide is MF5 and / or MCl5. When the trimethylsilyl dialkylamine Me3SiNR... 1 R 2 When the trimethylsilyl halide is Me3SiNEt2 (Et is ethyl, boiling point 125℃ to 126℃), the boiling point of the trimethylsilyl halide that escapes is below 125℃, which is conducive to the forward reaction. Considering the boiling point of the halide and the tantalum content in the halide, the preferred halide is MF5 and / or MCl5.

[0033] Therefore, the halide MX5 is preferably MF5 and / or MCl5.

[0034] Preferably, the R 1 With R 2 Each is independently methyl and / or ethyl.

[0035] Correspondingly, the trimethylsilyldialkylamine Me3SiNR 1 R 2 Preferably, it is any one or a combination of at least two of trimethylsilyldimethylamine, trimethylsilyldiethylamine, or trimethylsilylmethylethylamine.

[0036] The present invention relates to halide MX5 and trimethylsilyldialkylamine Me3SiNR 1 R 2 The reaction yields dialkylamino metal halide M(NR) 1 R 2 ) 5-n X n A solution, wherein n takes the value of 0 or 1. As a preferred embodiment, when n is 0, the trimethylsilyldialkylamine Me3SiNR... 1 R 2The molar ratio of the feed to halide MX5 should be ≥5:1. To ensure product formation efficiency, trimethylsilyldialkylamine Me3SiNR is preferred. 1 R 2 The molar ratio of the feed to halide MX5 is 5:1 to 12:1, for example, it can be 5:1, 6:1, 8:1, 10:1 or 12:1, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0037] In this invention, trimethylsilyldialkylamine Me3SiNR is used. 1 R 2 A molar ratio of MX5 to halide of 5:1 to 12:1 ensures complete conversion of MX5 to M(NR). 1 R 2 5. Reduce the formation of some dechlorination complexes.

[0038] Preferably, the mass ratio of the halide MX5 to the inert solvent is 1:4 to 1:40, for example, it can be 1:4, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35 or 1:40, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0039] The inert solvent in this invention is effective against MX5 and Me3SiNR. 1 R 2 It serves to disperse and dissolve.

[0040] Preferably, the inert solvent includes hydrocarbon solvents that do not participate in the reaction.

[0041] The inert solvent selected in this invention has a boiling point higher than that of trimethylsilane Me3SiX, thus avoiding excessive removal of the inert solvent while removing Me3SiX. Furthermore, to reduce solvent evaporation during purification, the inert solvent is preferably selected with a boiling point higher than that of Me3SiNR. 1 R 2 The inert solvent is a hydrocarbon solvent with a boiling point above 10°C; moreover, to facilitate the removal of the solvent after the reaction, the boiling point of the inert solvent needs to be controlled to not exceed 150°C. More preferably, the inert solvent is a hydrocarbon solvent with a boiling point between 60°C and 150°C, for example, 60°C, 70°C, 80°C, 90°C, 100°C, 120°C, or 150°C, but is not limited to the listed values; other unlisted values ​​within the range are also applicable.

[0042] Preferably, the inert solvent includes any one or a combination of at least two of the following: n-hexane (boiling point 68.9°C), n-heptane (boiling point 98°C), n-octane (boiling point 125°C), n-nonane (boiling point 151°C), n-decane (boiling point 174°C), toluene (boiling point 110°C), xylene, or trimethylbenzene.

[0043] The xylenes described in this invention include any one or a combination of at least two of p-xylene, m-xylene, or o-xylene. Typical but non-limiting combinations include combinations of p-xylene and m-xylene, m-xylene and o-xylene, p-xylene and o-xylene, or combinations of p-xylene, m-xylene, and o-xylene.

[0044] The trimethylbenzene described in this invention includes any one or a combination of at least two of mesitylene, pseudotrimethylbenzene, or trimethylbenzene. Typical but non-limiting combinations include a combination of mesitylene and pseudotrimethylbenzene, a combination of pseudotrimethylbenzene and trimethylbenzene, a combination of mesitylene and trimethylbenzene, or a combination of mesitylene, pseudotrimethylbenzene, and trimethylbenzene.

[0045] Preferably, the protective atmosphere uses nitrogen and / or an inert gas.

[0046] The reaction temperature in the first aspect of the present invention is preferably lower than that of trimethylsilyldialkylamine Me3SiNR. 1 R 2 Its boiling point is higher than that of trimethylsilane Me3SiX. To reduce Me3SiNR... 1 R 2 Precipitation in an inert solvent allows the reaction to proceed in the forward direction and avoids the precipitation of Me3SiNR. 1 R 2 The volatilization and escape are preferably carried out at a temperature of 0°C to 150°C, for example, 0°C, 20°C, 30°C, 50°C, 60°C, 80°C, 100°C, 120°C or 150°C, but not limited to the listed values. Other unlisted values ​​within the range are also applicable, with 20°C to 120°C being the preferred temperature.

[0047] For example, when trimethylsilyldialkylamine Me3SiNR 1 R 2 When the metal source is Me3SiNMe2, the reaction temperature should not exceed 84℃. If MF5 is selected as the metal source, the reaction temperature is preferably above 16℃ and not exceeding 84℃. If MCl5 is selected as the metal source, the reaction temperature is preferably above 57℃ and not exceeding 84℃.

[0048] For example, when trimethylsilyldialkylamine Me3SiNR 1 R 2When Me3SiNEt2 is used, the reaction temperature should not exceed 125℃. If MF5 is used as the metal source, the reaction temperature is preferably above 16℃ and not exceeding 125℃. If MCl5 is used as the metal source, the reaction temperature is preferably above 57℃ and not exceeding 125℃. If MBr4 is used as the metal source, the reaction temperature is preferably above 79℃ and not exceeding 84℃.

[0049] Preferably, the reaction time is from 3h to 30h, for example, it can be 3h, 5h, 8h, 10h, 12h, 15h, 16h, 18h, 20h, 24h, 25h, 28h or 30h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0050] Preferably, the reaction is carried out under stirring conditions.

[0051] Preferably, the stirring speed of the stirring conditions is from 30 rpm to 150 rpm, for example, it can be 30 rpm, 40 rpm, 50 rpm, 60 rpm, 80 rpm, 100 rpm, 120 rpm or 150 rpm, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0052] In a second aspect, the present invention provides a preparation apparatus system for preparing the dialkylamino metal halide described in the first aspect, the preparation apparatus system comprising a reaction unit, a pretreatment unit, a filtration unit, a purification unit and a nitrogen supply unit;

[0053] The reaction unit includes a reaction apparatus, a trimethylsilyldialkylamine supply device, and a halide supply device; the trimethylsilyldialkylamine supply device and the halide supply device are independently connected to the reaction apparatus through feed pipelines.

[0054] The nitrogen supply pipeline of the nitrogen supply unit is connected to the feed pipeline of the trimethylsilyldialkylamine supply device and the feed pipeline of the halide supply device, respectively.

[0055] The pretreatment unit includes a condensation device and a first vacuum generator connected in sequence; the condensation device includes at least one condenser connected in series, and the bottom outlet of the last condenser is connected to a light phase storage tank; the first vacuum generator is used to control the vacuum level of the condensation device.

[0056] The purification unit includes a sublimator, a fractionation device, a second vacuum generator, a first crystallization device, and a third vacuum generator; the light phase outlet of the sublimator is connected to the fractionation device; the second vacuum generator is used to control the vacuum level of the fractionation device; the sublimator is also connected to the first crystallization device; the third vacuum generator is used to control the vacuum level of the first crystallization device.

[0057] The discharge port of the reaction device and the inlet of the sublimator are each independently connected to the filtration unit.

[0058] When preparing the dialkylamino metal halide described in the first aspect using the preparation apparatus system provided in the second aspect:

[0059] (a) Nitrogen purging is performed on all units and connecting pipelines involved in the preparation apparatus system, and inert solvents, halides and trimethylsilyldialkylamine are prepared according to the feed amount;

[0060] (b) An inert solvent, a halide, and a trimethylsilyldialkylamine are mixed in the reaction apparatus, and the temperature inside the reaction apparatus is controlled to allow the reaction to proceed.

[0061] (c) After the low-boiling-point components are removed by distillation in the reaction apparatus, the product solution is filtered by the filtration unit and then enters the sublimator.

[0062] (d) The temperature and pressure of the sublimator are controlled to carry out vacuum distillation and sublimation. The inert solvent enters the fractionation unit from the light phase outlet above the sublimator and is collected in the heavy phase storage tank below the fractionation column. The dialkylamino metal halide is sublimated under vacuum and enters the first crystallization unit and is collected in the first product storage tank below the crystallizer.

[0063] For example, the reaction apparatus of the present invention is provided with a stirring device; the stirring device includes, but is not limited to, an anchor-type stirring device or a frame-type stirring device.

[0064] Preferably, the first fractionation apparatus includes a distillation column and a heavy phase storage tank;

[0065] The light phase outlet of the sublimator is connected to the feed inlet of the distillation column;

[0066] The heavy phase outlet of the distillation column is connected to the heavy phase storage tank;

[0067] Preferably, the first crystallization apparatus includes a first crystallizer and a first product storage tank;

[0068] The inert solvent is recovered in the heavy phase storage tank, and dialkylamino metal halide M(NR) is obtained in the first product storage tank. 1 R 2 ) 5-n X n .

[0069] Preferably, the filtration unit includes at least two filters connected in parallel; the outlet of the reaction device and the inlet of the sublimator are respectively connected to both ends of the filters.

[0070] For example, the filter is an atmospheric pressure filter or a pressurized filter.

[0071] Preferably, the connecting pipes between the filter and the reaction device and the connecting pipes between the filter and the sublimator are respectively connected to the nitrogen supply pipes of the nitrogen supply unit.

[0072] As a further preferred technical solution, the preparation method provided in the first aspect is carried out in the apparatus system provided in the second aspect.

[0073] Thirdly, the present invention provides a method for preparing an iminotris(dialkylamino) metal complex, the method comprising the following steps:

[0074] (1) Under a protective atmosphere, in an inert solvent, halide MX5 reacts with trimethylsilyldialkylamine Me3SiNR 1 R 2 The reaction yields a tetra(dialkylamino) halide solution, as shown in the following reaction equation:

[0075] MX5+Me3SiNR 1 R 2 →M(NR 1 R 2 )4X+Me3SiX;

[0076] (2) Under a protective atmosphere, trimethylsilyl monoalkylamine Me3SiNHR 3 Compared with the tetra(dialkylamino)halide M(NR) obtained in step (1) 1 R 2 The ligand exchange was performed using a 4X solution, and the product solution was purified to obtain the iminotris(dialkylamino)metal complex R. 3 N = M(NR) 1 R 2 3. The reaction formula is as follows:

[0077] M(NR 1 R 2 )4X+Me3SiNHR 3 →R 3 N = M(NR) 1 R 2 )3+Me3SiX+HNR 1 R 2 ;

[0078] M is a fifth subgroup element;

[0079] X is a halogen;

[0080] The R 1 R 2 With R 3 Each is independently hydrogen-based and / or alkyl-based, where N is an amino nitrogen and Me is a methyl group.

[0081] In the preparation method of the tri(dialkylamino) metal complex provided by this invention, trimethylsilyldialkylamine Me3SiNR 1 R 2 As a reactant, it provides a dialkylamino ligand and also acts as a dehalogenating agent for the halide MX5. The dehalogenated product Me3SiX escapes in gaseous form during the reaction, which favors the forward reaction. Therefore, the boiling point of Me3SiX is particularly important for promoting the forward reaction. Based on the formation rate of Me3SiX, to advance the reaction forward, trimethylsilyldialkylamine Me3SiNR... 1 R 2 It can be added in batches or by dripping.

[0082] In this invention, M is a group 5 element, including but not limited to tantalum or niobium.

[0083] For example, the melting and boiling points of trimethylsilyl halides are as follows: Me3SiF has a melting point of -74°C and a boiling point of 16°C; Me3SiCl has a melting point of -40°C and a boiling point of 57°C; Me3SiBr has a melting point of -43°C and a boiling point of 79°C; and Me3SiI has a melting point <0°C and a boiling point of 106°C. When the byproduct Me3SiX escapes in gaseous form during the reaction, the trimethylsilyldialkylamine reactant, which serves as a dehalogenating agent, preferably remains in the system to continue the reaction. Therefore, trimethylsilyldialkylamine Me3SiNR is preferred. 1 R 2 Its boiling point is higher than that of the byproduct trimethylsilyl halide.

[0084] For example, when trimethylsilyldialkylamine Me3SiNR 1 R 2 When the reaction is Me3SiNMe2 (boiling point 84℃), the boiling point of the released trimethylsilyl halide is below 84℃, which favors the forward reaction. In this case, the preferred halide is MF5 and / or MCl5. When the trimethylsilyl dialkylamine Me3SiNR... 1 R 2 When the trimethylsilyl halide is Me3SiNEt2 (Et is ethyl, boiling point 125℃ to 126℃), the boiling point of the trimethylsilyl halide that escapes is below 125℃, which is conducive to the forward reaction. Considering the boiling point of the halide and the tantalum content in the halide, the preferred halide at this time is MF5 and / or MCl5.

[0085] Therefore, the halide MX5 includes MF5 and / or MCl5.

[0086] Preferably, the R 1 With R 2 Each is independently methyl and / or ethyl.

[0087] Correspondingly, the trimethylsilyldialkylamine Me3SiNR 1 R 2 Preferably, it is any one or a combination of at least two of trimethylsilyldimethylamine, trimethylsilyldiethylamine, or trimethylsilylmethylethylamine; the tetra(dialkylamino)halide M(NR) 1 R 2 4X is preferably any one or a combination of at least two of tetra(dimethylamino)halides, tetra(diethylamino)halides, or tetra(methylethylamino)halides.

[0088] Preferably, the R 3 It is any one or a combination of at least two of tert-butyl, tert-pentyl, isopropyl, cyclohexyl, or cyclopentyl.

[0089] Correspondingly, the trimethylsilyl monoalkylamine Me3SiNHR 3 Preferably, trimethylsilyl-tert-butylamine, trimethylsilyl-tert-pentylamine, trimethylsilyl-isopropylamine, trimethylsilyl-cyclohexylamine, and / or trimethylsilyl-cyclopentylamine are used; the resulting iminotris(dialkylamino)metal complex R 3 N = M(NR) 1 R 2 )3 is t BuN=M(NR 1 R 2 3. t AmN=M(NR 1 R 2 3. i PrN=M(NR 1 R 2 3. CyN = M(NR) 1 R 2 )3 or CpN = M(NR 1 R 2 Any one of the three or a combination of the qualities.

[0090] To ensure that the MX5 is fully converted to M(NR) 1 R 2 )4X, reducing the formation of metal-containing complexes in other dehalogenation processes, the trimethylsilyl dialkylamine Me3SiNR in the preparation method of tri(dialkylamino)metal complexes provided by this invention. 1 R 2 The feeding ratio must be strictly controlled. When Me3SiNR 1 R 2 When the molar ratio of feed to MX5 is less than 4:1, a considerable proportion of M(NR) will be produced. 1 R 2)3X2 or M(NR) 1 R 2 )2x3 or even MNR 1 R 2 X4 is generated, and then combined with Me3SiNHR 3 When the reaction occurs, bisimino compounds or even more complex metal-containing complexes are obtained. When Me3SiNR 1 R 2 When the molar ratio of MX5 to MX5 is higher than 4.2:1, M(NR) will be dehalogenated to varying degrees or even completely. 1 R 2 )5 is generated, and then combined with Me3SiNHR 3 When a reaction occurs, the following reactions often take place:

[0091] M(NR 1 R 2 )5+Me3SiNHR 3 →R 3 N = M(NR) 1 R 2 )3+Me3SiNR 1 R 2 +HNR 1 R 2 ;

[0092] To ensure the reaction favors R 3 N = M(NR) 1 R 2 The generation of )3 requires timely removal of Me3SiNR. 1 R 2 However, Me3SiNHR 3 The boiling point is not always higher than that of Me3SiNR 1 R 2 (e.g. Me3SiNH) i Pr has a boiling point of 98℃, Me3SiNH t The boiling point of Bu is approximately 118°C to 119°C, making it possible to remove Me3SiNR by distillation. 1 R 2 It becomes difficult, and increasing the temperature will cause the reactant Me3SiNHR to become difficult to react. 3 They were removed together. In the intermediate substance M(NR) 1 R 2 Based on 4X, ligand exchange was performed to generate Me3SiX and HNR. 1 R 2 Its low boiling point makes it easy to remove by distillation, which makes the reaction proceed easily in the forward direction.

[0093] Therefore, trimethylsilyldialkylamine Me3SiNR is preferred. 1 R 2The molar ratio of the feed to halide MX5 is 4:1 to 4.2:1, for example, it can be 4:1, 4.05:1, 4.1:1, 4.15:1 or 4.2:1, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0094] In addition to providing dialkylamino ligands and acting as a dehalogenating agent, trimethylsilyl dialkylamine can also function as a chemical dehydrating agent in the reaction. When trace amounts of water are present in the system, the following reaction occurs:

[0095] 2Me3SiNR 1 R 2 +H₂O→Me₃Si-O-SiMe₃+2HNR 1 R 2 ;

[0096] As can be seen from the reaction equation, one water molecule can be reacted by two molecules of Me3SiNR. 1 R 2 Consumption yields dialkylamine and hexamethyldisiloxane.

[0097] Preferably, the reaction temperature in step (1) is lower than that of trimethylsilyldialkylamine Me3SiNR. 1 R 2 The boiling point of the reaction; more preferably, the temperature of the reaction in step (1) is higher than the boiling point of trimethylsilane Me3SiX.

[0098] Preferably, the temperature of the reaction in step (1) is from 0°C to 150°C, for example, it can be 0°C, 10°C, 30°C, 50°C, 60°C, 80°C, 100°C, 120°C or 150°C, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0099] Me3SiNR 1 R 2 The dehalogenation reaction with MX5 can be carried out in a temperature range of 0°C to 150°C. When the reaction temperature in step (1) is below 0°C, Me3SiNR is present. 1 R 2 Precipitation in inert solvents can cause problems and reduce the volatility of Me3SiX, affecting the smooth progress of the reaction. Higher reaction temperatures favor the forward reaction and reduce the formation of metal-containing complexes in other dehalogenation processes, thus promoting the formation of tetra(dialkylamino)halides. However, the temperature should not exceed that of Me3SiNR. 1 R 2 The boiling point, otherwise it will lead to Me3SiNR 1 R 2Escape can prevent the dehalogenation reaction from proceeding smoothly and may also damage the intermediate tetra(dialkylamino)halides. Therefore, the temperature of the reaction in step (1) is preferably 20°C to 120°C.

[0100] Preferably, the reaction time in step (1) is 3h to 30h, for example, it can be 3h, 5h, 8h, 10h, 15h, 20h, 25h or 30h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0101] Preferably, the halide MX5 and the trimethylsilyl monoalkylamine Me3SiNHR 3 The molar ratio of the feed is 1:1 to 1:1.1, for example, it can be 1:1, 1:1.05 or 1:1.1, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0102] To generate iminotris(dialkylamino)metal complex R 3 N = M(NR) 1 R 2 3. During the reaction, the locene monomers must be fed in strict accordance with the stoichiometric ratio. If Me3SiNHR 3 Insufficient feed will result in product R 3 N = M(NR) 1 R 2 The amount of )3 produced decreases; if Me3SiNHR 3 Excessive feeding can lead to the formation of polyimide-substituted metal complexes (e.g., R...). 3 N=)2MNR 1 R 2 )generate.

[0103] More preferably, the trimethylsilyl monoalkylamine in step (2) is added dropwise to the tetra(dialkylamino)halide M(NR). 1 R 2 Mixing 4X solutions avoids the presence of Me3SiNHR in the reaction system. 3 Excessive local concentration of [agent] should be avoided to prevent the formation of metal complexes with polyimide substitution.

[0104] Preferably, the ligand exchange temperature in step (2) is lower than that of Me3SiNHR. 3 The boiling point; more preferably, the ligand exchange temperature in step (2) is higher than that of trimethylhalosilane Me3SiX and dialkylamine HNR. 1 R 2 The boiling point of .

[0105] Preferably, the temperature for ligand exchange in step (2) is from -20°C to 150°C, for example, it can be -20°C, -10°C, 0°C, 10°C, 30°C, 50°C, 60°C, 80°C, 100°C, 120°C or 150°C, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0106] M(NR 1 R 2 )4X and Me3SiNHR 3 The ligand exchange reaction can proceed in a temperature range from -20°C to 150°C. The minimum temperature for ligand exchange depends on the melting point of the inert solvent, but when the temperature is below -20°C, the rate of ligand exchange slows down and the reaction efficiency decreases. For ligand exchange reactions, higher reaction temperatures favor product formation, especially for ligand exchange reactions above those of dialkylamines (HNR). 1 R 2 When the boiling point of Me3SiX is reached, it is beneficial to HNR. 1 R 2 The volatilization and release of Me3SiX facilitates the forward progression of the ligand exchange reaction; however, the temperature of the ligand exchange reaction should not exceed Me3SiNHR. 3 The boiling point, otherwise Me3SiNHR 3 A large amount of volatilization and escape affects the efficiency of ligand exchange.

[0107] Me3SiNH i Pr has a boiling point of 98℃, Me3SiNH t The boiling point of Bu is 118–119 °C. The boiling point of dimethylamine is 7 °C, that of diethylamine is 55 °C, and that of methylethylamine is 36–37 °C. The boiling point of Me3SiF is 16 °C, that of Me3SiCl is 57 °C, that of Me3SiBr is 79 °C, and that of Me3SiI is 106 °C.

[0108] For example, when the trimethylsilyl monoalkylamine is Me3SiNH i When Pr is used, the ligand exchange temperature should not exceed 98°C, and is preferably 0°C to 98°C; if the intermediate product is M(NMe2)4F, the ligand exchange temperature is preferably 16°C to 98°C; if the intermediate product is M(NEtMe)4Cl, the ligand exchange temperature is preferably 57°C to 98°C.

[0109] For example, when the trimethylsilyl monoalkylamine is Me3SiNH tWhen Bu is used, the ligand exchange temperature should not exceed 119°C, and is preferably 0°C to 119°C; if the intermediate product is M(NMe2)4Br, the ligand exchange temperature is preferably 79°C to 119°C; if the intermediate product is M(NEtMe)4F, the ligand exchange temperature is preferably 36°C to 119°C; if the intermediate product is M(NEt2)4Cl, the ligand exchange temperature is preferably 57°C to 119°C.

[0110] The temperature of ligand exchange in step (2) of this invention can be a constant temperature or it can vary within a temperature range during the ligand exchange process.

[0111] Preferably, the ligand exchange time in step (2) is 2h to 20h, for example, it can be 2h, 4h, 5h, 8h, 10h, 12h, 15h, 18h or 20h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0112] Preferably, the inert solvent in step (1) includes a hydrocarbon solvent that does not participate in the reaction; more preferably, it is a hydrocarbon solvent with a boiling point below 150°C; and more preferably, it is a hydrocarbon solvent with a boiling point above trimethylsilyldialkylamine Me3SiNR. 1 R 2 Hydrocarbon solvents with a boiling point above 10°C.

[0113] The inert solvent in step (1) of this invention serves to disperse the reactants; although MX5 and Me3SiNR 1 R 2 It can react even in the absence of a solvent, but due to the dispersion and dissociation in the absence of a solvent, it is easy to form metal-containing complexes that are partially dehalogenated, making it difficult to fully dehalogenate and form M(NR). 1 R 2 )4X; and during the Me3SiNHR process 3 During ligand exchange reactions, additional solvent is required for dispersion.

[0114] The inert solvent selected in this invention preferably has a boiling point higher than that of the trimethylsilane Me3SiX, to avoid excessive removal of the inert solvent during the removal of Me3SiX and to prevent the need for additional inert solvent replenishment. Furthermore, to reduce solvent evaporation during purification, the inert solvent is preferably selected with a boiling point higher than that of Me3SiNR. 1 R 2 Hydrocarbon solvents with a boiling point above 10°C are required; moreover, in order to facilitate the removal of the solvent after the reaction, the boiling point of the inert solvent needs to be controlled to not exceed 150°C.

[0115] Preferably, the inert solvent in step (1) includes any one or a combination of at least two of the following: n-hexane (boiling point 69°C), n-heptane (boiling point 98°C), n-octane (boiling point 125°C), toluene (boiling point 110°C), o-xylene (boiling point 144.4°C), or m-xylene (boiling point 138°C). Typical but non-limiting combinations include combinations of n-heptane and n-octane, n-octane and toluene, toluene and o-xylene, o-xylene and m-xylene, n-heptane, n-octane and toluene, toluene, o-xylene and m-xylene, or n-heptane, n-octane, toluene, o-xylene and m-xylene.

[0116] Preferably, the mass ratio of the halide MX5 to the inert solvent in step (1) is 1:4 to 1:40, for example, it can be 1:4, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35 or 1:40, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0117] In order to ensure the uniform and stable dispersion of MX5 and reduce the formation of metal-containing complexes in other dehalogenated parts, the mass ratio of MX5 to inert solvent should not be less than 1:4. In order to ensure the product formation efficiency, the mass ratio of MX5 to inert solvent should not exceed 1:40.

[0118] Preferably, the protective atmosphere uses nitrogen and / or an inert gas.

[0119] Preferably, the reaction in step (1) and / or the ligand exchange in step (2) are carried out under stirring conditions.

[0120] Preferably, the stirring speed of the stirring conditions is from 30 rpm to 150 rpm, for example, it can be 30 rpm, 40 rpm, 50 rpm, 60 rpm, 80 rpm, 100 rpm, 120 rpm or 150 rpm, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0121] Fourthly, the present invention provides an apparatus system for preparing iminotris(dialkylamino) metal complexes, the apparatus system comprising a reaction unit, a pretreatment unit, a filtration unit, a purification unit and a nitrogen supply unit;

[0122] The reaction unit includes a reaction apparatus, a trimethylsilyl dialkylamine supply device, a halide supply device, and a trimethylsilyl monoalkylamine supply device; the trimethylsilyl dialkylamine supply device, the halide supply device, and the trimethylsilyl monoalkylamine supply device are each independently connected to the reaction apparatus through a feed pipeline.

[0123] The nitrogen supply pipeline of the nitrogen supply unit is connected to the feed pipeline of the trimethylsilyldialkylamine supply device and the feed pipeline of the halide supply device, respectively.

[0124] The pretreatment unit includes a condensation device and a first vacuum generator connected in sequence; the condensation device includes at least one condenser connected in series, and the bottom outlet of the last condenser is connected to a light phase storage tank; the first vacuum generator is used to control the vacuum level of the condensation device.

[0125] The purification unit includes a sublimator, a fractionation device, a second vacuum generator, a first crystallization device, a second crystallization device, and a third vacuum generator; the light phase outlet of the sublimator is connected to the fractionation device; the second vacuum generator is used to control the vacuum level of the fractionation device; the sublimator is also connected to the first crystallization device and the second crystallization device; the third vacuum generator is used to control the vacuum level of the first crystallization device and the second crystallization device.

[0126] The discharge port of the reaction device and the inlet of the sublimator are each independently connected to the filtration unit.

[0127] When preparing tris(dialkylamino)tantalum complexes using the preparation apparatus system provided in the fourth aspect:

[0128] For example, the reaction apparatus of the present invention is provided with a stirring device; the stirring device includes, but is not limited to, an anchor-type stirring device or a frame-type stirring device.

[0129] Preferably, the fractionation apparatus includes a distillation column and a heavy phase storage tank;

[0130] The light phase outlet of the sublimator is connected to the feed inlet of the distillation column, and the heavy phase outlet of the distillation column is connected to the heavy phase storage tank.

[0131] The first crystallization apparatus includes a first crystallizer and a first product storage tank, and the second crystallization apparatus includes a second crystallizer and a second product storage tank; the first product storage tank is connected to the bottom of the first crystallizer and a third vacuum generator is connected to the top of the first crystallizer; the second product storage tank is connected to the bottom of the second crystallizer and a third vacuum generator is connected to the top of the second crystallizer.

[0132] The inert solvent is recovered in the heavy phase storage tank, and tetra(dialkylamino)halide M(NR) is obtained in the first product storage tank. 1 R 2 )4X, the iminotris(dialkylamino) metal complex R was obtained in the second product storage tank. 3 N = M(NR) 1 R 2 3.

[0133] Preferably, the filtration unit includes at least two filters connected in parallel; the outlet of the reaction device and the inlet of the sublimator are respectively connected to both ends of the filters.

[0134] Preferably, the connecting pipes between the filter and the reaction device and the connecting pipes between the filter and the sublimator are respectively connected to the nitrogen supply pipes of the nitrogen supply unit.

[0135] As a further preferred technical solution, the preparation method provided in the third aspect is carried out in the preparation apparatus system provided in the fourth aspect.

[0136] Compared with the prior art, the present invention has the following beneficial effects:

[0137] (1) The method for preparing dialkylamino metal halides provided by the present invention utilizes trimethylsilyl dialkylamine to completely dehalogenate the halides. The reaction is easy to control, the operation is simple, and no solid waste such as lithium halides that are difficult to separate is generated. The product obtained has high purity and is easy to realize industrial production.

[0138] (2) The method for preparing iminotris(dialkylamino) metal complexes provided by the present invention is to fully dehalogenate halides with trimethylsilyldialkylamine to prepare intermediate tetra(dialkylamino) halides, and then perform ligand exchange with trimethylsilylmonoalkylamine to prepare the product. This method is a solid-liquid reaction between halides and dehalogenating agents, which is different from the solid-solid reaction between lithium alkylamino and halides. It is easier to disperse evenly. Within the boiling point range allowed by the dehalogenating agent, the dehalogenation reaction can be carried out at a higher temperature and the reaction rate is faster. This method can avoid the metal impurities introduced by the impure n-butyllithium used in the lithium alkylamino technical route, and can also avoid the generation of solid wastes such as lithium salts that are not easy to separate later. It facilitates product purification and the obtained product is easy to meet the purity requirements of precursor materials in integrated circuit manufacturing.

[0139] Trimethylsilyldialkylamine serves as a reactant, acting as a dehalogenating agent for halides, a donor of dialkylamino ligands, and a chemical dehydrating agent. Adding a slight excess of trimethylsilyldialkylamine during the reaction ensures complete dehalogenation of the halides and removes trace amounts of moisture remaining in the reaction apparatus and materials, thus facilitating product formation. Using trimethylsilyl monoalkylamine as a primary amine donor allows for a faster reaction rate at higher temperatures within the permissible boiling point range.

[0140] (3) The reaction apparatus for preparing high-purity dialkylamino metal halides and iminotris(dialkylamino) metal complexes provided by the present invention adopts the technical route of trimethylsilyldialkylamine, which does not require strict stoichiometric ratio of n-butyllithium or dialkylaminolithium as the technical route of dialkylaminolithium. The reaction conditions are easy to control. The reaction unit and the purification unit are used in combination in the apparatus. In addition to purifying the product, the by-products, unreacted trimethylsilyldialkylamine and solvent can also be recovered. At the same time, low-boiling-point dialkylamine and trimethylhalosilane are collected for regenerating trimethylsilyldialkylamine. Attached Figure Description

[0141] Figure 1 This is a schematic diagram of the device system for the iminotris(dialkylamino) metal complex provided by the present invention.

[0142] Wherein: 11, reaction apparatus; 12, trimethylsilyl dialkylamine supply device; 13, halide mixing tank; 14, solvent tank; 15, trimethylsilyl monoalkylamine supply device;

[0143] 21, front condenser; 22, rear condenser; 23, light phase storage tank; 24, first cold trap; 25, first vacuum generator;

[0144] 31, First filter; 32, Second filter;

[0145] 41, Sublimator; 42, Waste tank; 43, Fractionation unit; 44, Heavy phase storage tank; 45, Second cold trap; 46, Second vacuum generator; 47, First crystallization unit; 48, First product storage tank; 49, Second crystallization unit; 410, Second product storage tank; 411, Third cold trap; 412, Third vacuum generator. Detailed Implementation

[0146] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0147] In the specific embodiments of the present invention, the methods for preparing dialkylamino metal halides and iminotris(dialkylamino) metal complexes can both be implemented as follows: Figure 1 The preparation of iminotris(dialkylamino) metal complexes is carried out in the apparatus system shown. That is, the apparatus system for preparing dialkylamino metal halides and the apparatus system for preparing iminotris(dialkylamino) metal complexes share common parts; when using the apparatus system for preparing iminotris(dialkylamino) metal complexes to prepare dialkylamino metal halides, only the corresponding apparatus units need to be used.

[0148] like Figure 1The apparatus system for the iminotris(dialkylamino) metal complex shown includes a reaction unit, a pretreatment unit, a filtration unit, a purification unit, and a nitrogen supply unit;

[0149] The reaction unit includes a reaction device 11, a trimethylsilyl dialkylamine supply device 12, a halide supply device, and a trimethylsilyl monoalkylamine supply device; the trimethylsilyl dialkylamine supply device 12, the halide supply device, and the trimethylsilyl monoalkylamine supply device are each independently connected to the reaction device 11 through a feed pipeline.

[0150] The halide supply device includes a solvent tank 14 and a halide mixing tank 13. The solvent outlet of the solvent tank 14 is connected to the halide mixing tank 13, and the outlet of the halide mixing tank 13 is connected to the reaction device 11 through a feed pipe.

[0151] The nitrogen supply pipeline of the nitrogen supply unit is connected to the feed pipeline of the trimethylsilyldialkylamine supply device 12 and the feed pipeline of the halide supply device, respectively.

[0152] The pretreatment unit includes a condensing device and a first vacuum generating device 25 connected in sequence; the condensing device includes a front condenser 21 and a rear condenser 22 connected in series, and the bottom outlet of the rear condenser 22 is connected to a light phase storage tank 23; the first vacuum generating device 25 is used to control the vacuum degree of the condensing device; a first cold trap 24 is provided between the first vacuum generating device 25 and the condenser to protect the first vacuum generating device 25.

[0153] The purification unit includes a sublimator 41, a waste tank 42, a fractionation device 43, a second vacuum generator 46, a first crystallization device 47, a second crystallization device 49, and a third vacuum generator 412; the light phase outlet of the sublimator 41 is connected to the fractionation device 43, and the bottom outlet of the sublimator 41 is connected to the waste tank 42; the second vacuum generator 46 is used to control the vacuum degree of the fractionation device 42; the connecting pipeline between the second vacuum generator 46 and the fractionation device 43 is provided with a second cold trap 45 to protect the second vacuum generator 46;

[0154] The bottom outlet of the fractionation device 43 is connected to the heavy phase storage tank 44; the sublimator 41 is connected to the first crystallization device 47 and the second crystallization device 49 respectively; the third vacuum generator 412 is used to control the vacuum degree of the first crystallization device 47 and the second crystallization device 49; the lower outlet of the first crystallization device 47 is connected to the first product storage tank 48, and the lower outlet of the second crystallization device 49 is connected to the second product storage tank 410; the connecting pipeline between the third vacuum generator 412 and the first crystallization device 47 and the second crystallization device 49 is equipped with a third cold trap 411 to protect the third vacuum generator 412;

[0155] The outlet of the reaction device 11 and the inlet of the sublimator 41 are independently connected to the filtration unit; the filtration unit includes two parallel-connected first filters 31 and second filters 32; the outlet of the reaction device 11 and the inlet of the sublimator 41 are respectively connected to the two ends of the filters.

[0156] The inert solvent is recovered in the heavy phase storage tank 44, and the dialkylamino metal halide M(NR) is obtained in the first product storage tank 48. 1 R 2 ) 5-n X n Iminotris(dialkylamino) metal complex R was obtained in the second product storage tank 410. 3 N = M(NR) 1 R 2 3.

[0157] The connecting pipes between the filter and the reaction device 11 and between the filter and the sublimator 41 are respectively connected to the nitrogen supply pipes of the nitrogen supply unit.

[0158] The preparation of iminotris(dialkylamino) metal complexes using an apparatus system includes the following steps:

[0159] (a) Nitrogen purging is performed on all units and connecting pipelines involved in the preparation apparatus system, and inert solvents, halides, trimethylsilyldialkylamines and trimethylsilylmonoalkylamines are prepared according to the feed amount;

[0160] (b) A portion of the inert solvent in the solvent tank is dispersed with the halide in the halide mixing tank 13 and transferred to the reaction apparatus 11. Then, the remaining solvent is used to rinse the halide mixing tank 13 and transferred to the reaction apparatus 11. Trimethylsilyldialkylamine is added to the reaction apparatus 11, and the temperature inside the reaction apparatus 11 is controlled to allow the reaction to proceed. After the reaction is completed, the generated trimethylhalosilane is removed by distillation. The temperature inside the reaction apparatus 11 is adjusted to below the boiling point of the trimethylsilylmonoalkylamine. Trimethylsilylmonoalkylamine is added to carry out the ligand exchange reaction.

[0161] (c) After the low-boiling-point components are removed by distillation in the reaction apparatus 11, the product solution is filtered by the filtration unit and then enters the sublimator 41.

[0162] (d) The temperature and pressure of the sublimator 41 are controlled to carry out vacuum distillation. The inert solvent enters the fractionation device from the light phase outlet above the sublimator 41. The inert solvent is recovered through the fractionation device. The dialkylamino metal halide in the solid in the sublimator 41 is processed by the first crystallization device 47 and collected in the first product storage tank 48. The iminotris(dialkylamino) metal complex in the remaining solid is processed by the second crystallization device 49 and collected in the second product storage tank 410.

[0163] Example 1-1

[0164] This embodiment provides a method for preparing penta(dimethylamino)tantalum, the method comprising the following steps:

[0165] Under nitrogen atmosphere, in a 1L reaction apparatus, 35.8g (0.10mol) TaCl5 and 88.0g (0.75mol) Me3SiNMe2 were reacted in 358g (523mL) of inert solvent n-heptane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNMe2 was heated and distilled to obtain a pentapenta(dimethylamino)tantalum Ta(NMe2)5 solution.

[0166] The obtained penta(dimethylamino)tantalum Ta(NMe2)5 solution was subjected to vacuum distillation and sublimation in a sublimator to obtain penta(dimethylamino)tantalum in a first crystallization apparatus.

[0167] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0168] In this embodiment, the molar ratio of Me3SiNMe2 to TaCl5 is 7.5:1; the mass ratio of TaCl5 to n-heptane is 1:10.

[0169] Examples 1-2

[0170] This embodiment provides a method for preparing penta(dimethylamino)tantalum, the method comprising the following steps:

[0171] Under nitrogen atmosphere, in a 1L reaction apparatus, 71.64g (0.20mol) TaCl5 and 117.3g (1.00mol) Me3SiNMe2 were reacted in 287g (419mL) of inert solvent n-heptane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNMe2 was heated and distilled to obtain a pentapenta(dimethylamino)tantalum Ta(NMe2)5 solution.

[0172] The obtained penta(dimethylamino)tantalum Ta(NMe2)5 solution was subjected to vacuum distillation and sublimation in a sublimator to obtain penta(dimethylamino)tantalum in a first crystallization apparatus.

[0173] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0174] In this embodiment, the molar ratio of Me3SiNMe2 to TaCl5 is 5:1; the mass ratio of TaCl5 to n-heptane is 1:4.

[0175] Examples 1-3

[0176] This embodiment provides a method for preparing penta(dimethylamino)tantalum, the method comprising the following steps:

[0177] Under nitrogen atmosphere, in a 1L reaction apparatus, 10.75g (0.03mol) TaCl5 and 42.2g (0.36mol) Me3SiNMe2 were reacted in 430g (628mL) of inert solvent n-heptane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNMe2 was heated and distilled to obtain a pentapenta(dimethylamino)tantalum Ta(NMe2)5 solution.

[0178] The obtained penta(dimethylamino)tantalum Ta(NMe2)5 solution was subjected to vacuum distillation and sublimation in a sublimator to obtain penta(dimethylamino)tantalum in a first crystallization apparatus.

[0179] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0180] In this embodiment, the molar ratio of Me3SiNMe2 to TaCl5 is 12:1; the mass ratio of TaCl5 to n-heptane is 1:40.

[0181] Examples 1-4

[0182] This embodiment provides a method for preparing penta(methylethylamino)tantalum, except that the molar amount of Me3SiNMe2 is replaced with Me3SiNEtMe and the mass of n-heptane is replaced with n-octane, and the rest are the same as in Example 1-1.

[0183] Examples 1-5

[0184] This embodiment provides a method for preparing penta(diethylamino)tantalum, which is the same as in Example 1-1 except that the molar amount of Me3SiNMe2 is replaced with Me3SiNEt2 and the mass of n-heptane is replaced with n-nonane.

[0185] Examples 1-6

[0186] This embodiment provides a method for preparing penta(dimethylamino)tantalum, the method comprising the following steps:

[0187] Under nitrogen atmosphere, in a 1L reaction apparatus, 35.8g (0.130mol) TaF5 and 114.2g (0.974mol) Me3SiNMe2 were reacted in 358g (543mL) of inert solvent n-hexane. After the byproduct Me3SiF stopped distilling out, the unreacted Me3SiNMe2 was heated and distilled to obtain a pentapentan(dimethylamino)tantalum Ta(NMe2)5 solution.

[0188] The obtained penta(dimethylamino)tantalum Ta(NMe2)5 solution was subjected to vacuum distillation and sublimation in a sublimator to obtain penta(dimethylamino)tantalum in a first crystallization apparatus.

[0189] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0190] In this embodiment, the molar ratio of Me3SiNMe2 to TaF5 is 7.5:1; the mass ratio of TaF5 to n-hexane is 1:10.

[0191] Examples 1-7

[0192] This embodiment provides a method for preparing penta(dimethylamino)tantalum, the method comprising the following steps:

[0193] Under nitrogen atmosphere, in a 1L reaction apparatus, 35.8g (61.7mmol) TaBr5 and 54.3g (0.463mol) Me3SiNMe2 were reacted in 358g (411mL) of inert solvent toluene. The unreacted Me3SiNMe2 and the generated byproduct Me3SiBr were distilled by heating to obtain a pentapenta(dimethylamino)tantalum Ta(NMe2)5 solution.

[0194] The obtained penta(dimethylamino)tantalum Ta(NMe2)5 solution was subjected to vacuum distillation and sublimation in a sublimator, and penta(dimethylamino)tantalum was obtained in the first fractionation device.

[0195] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 80℃ and the reaction time was 6 h.

[0196] In this embodiment, the molar ratio of Me3SiNMe2 to TaBr5 is 7.5:1; the mass ratio of TaBr5 to toluene is 1:10.

[0197] Examples 1-8

[0198] This embodiment provides a method for preparing penta(dimethylamino)tantalum. Except for changing the amount of Me3SiNMe2 to make the molar ratio of Me3SiNMe2 to TaCl5 4:1, the rest is the same as in Example 1-1.

[0199] In this embodiment, no product was generated because TaCl5 was not completely dechlorinated.

[0200] Examples 1-9

[0201] This embodiment provides a method for preparing pentapenta(dimethylamino)tantalum. Except for changing the amount of Me3SiNMe2 to make the molar ratio of Me3SiNMe2 to TaCl5 13:1, the rest is the same as in Examples 1-3.

[0202] In this embodiment, the amount of Me3SiNMe2 added was too large, which affected the product preparation efficiency.

[0203] Examples 1-10

[0204] This embodiment provides a method for preparing penta(dimethylamino)tantalum. Except for changing the amount of n-heptane to make the mass ratio of TaCl5 to n-heptane 1:3, the rest is the same as in Examples 1-2.

[0205] Examples 1-11

[0206] This embodiment provides a method for preparing penta(dimethylamino)tantalum. Except for changing the amount of n-heptane to make the mass ratio of TaCl5 to n-heptane 1:42, the rest is the same as in Examples 1-3.

[0207] In this embodiment, the amount of n-heptane added was too large, which affected the product preparation efficiency.

[0208] The mass, yield calculated based on tantalum halide feed, and HPLC purity of the dialkylamino metal halides prepared in the above examples were determined, and the results are shown in Table 1.

[0209] Table 1

[0210] Example 1-1 35.7 89 99.99 Examples 1-2 65.8 82 99.2 Examples 1-3 10.5 87 99.99 Examples 1-4 41.5 88 99.99 Examples 1-5 46.6 86 99.99 Examples 1-6 46.4 89 99.99 Examples 1-7 18.6 75 99.8 Examples 1-8 —— —— —— Examples 1-9 10.6 88 99.99 Examples 1-10 66.6 83 98.3 Examples 1-11 10.6 88 99.99

[0211] The “——” in Table 1 indicates that no product was generated in Examples 1-8, therefore no relevant measurement results were obtained.

[0212] Example 2-1

[0213] This embodiment provides a method for preparing an iminotris(dimethylamino)tantalum complex, the method comprising the following steps:

[0214] (1) Under nitrogen atmosphere, in a 1L reaction apparatus, 35.8g (0.10mol) TaCl5 and 48.1g (0.41mol) Me3SiNMe2 reacted in 358g (523mL) of inert solvent n-heptane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNMe2 was heated and distilled to obtain a tetra(dimethylamino)tantalum chloride Ta(NMe2)4Cl solution.

[0215] The obtained tetra(dimethylamino)tantalum chloride Ta(NMe2)4Cl solution was subjected to vacuum distillation and sublimation in a sublimator to obtain tetra(dimethylamino)tantalum chloride in the first crystallization apparatus;

[0216] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0217] (2) Under a nitrogen atmosphere, the temperature was maintained at 60°C to prepare 15.4 g (0.106 mol) of trimethylsilyl tert-butylamine Me3SiNH. t Bu was added dropwise with continuous stirring during the addition process. After 2 hours of addition, ligand exchange was performed to obtain the product solution.

[0218] Ligand exchange was carried out under stirring conditions at a stirring speed of 100 rpm; the ligand exchange temperature was 60℃ for 2 h, followed by 80℃ for 2 h.

[0219] The resulting product solution was subjected to vacuum distillation and sublimation in a sublimator, and the tert-butyliminotris(dimethylamino)tantalum complex was obtained in a second crystallization apparatus. t BuN=Ta(NMe2)3.

[0220] In this embodiment, the molar ratio of Me3SiNMe2 to TaCl5 is 4.1:1; the mass ratio of TaCl5 to n-heptane is 1:10; and the mass ratio of TaCl5 to Me3SiNH2 is... t The molar ratio of Bu to feed is 1:1.06.

[0221] Example 2-2

[0222] This embodiment provides a method for preparing an iminotris(dimethylamino)tantalum complex, the method comprising the following steps:

[0223] (1) Under nitrogen atmosphere, in a 1L reaction apparatus, 71.6g (0.20mol) TaCl5 and 93.8g (0.80mol) Me3SiNMe2 were reacted in 287g (419mL) of inert solvent n-heptane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNMe2 was heated and distilled to obtain a tetra(dimethylamino)tantalum chloride Ta(NMe2)4Cl solution.

[0224] The obtained tetra(dimethylamino)tantalum chloride Ta(NMe2)4Cl solution was subjected to vacuum distillation and sublimation in a sublimator to obtain tetra(dimethylamino)tantalum chloride in the first crystallization apparatus;

[0225] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0226] (2) Under a nitrogen atmosphere, the temperature was maintained at 60°C to prepare 29.1 g (0.20 mol) of trimethylsilyl tert-butylamine Me3SiNH. t Bu was added dropwise with continuous stirring during the addition process. After 2 hours of addition, ligand exchange was performed to obtain the product solution.

[0227] Ligand exchange was carried out under stirring conditions at a stirring speed of 100 rpm; the ligand exchange temperature was 60℃ for 2 h, followed by 80℃ for 2 h.

[0228] The resulting product solution was subjected to vacuum distillation and sublimation in a sublimator, and the tert-butyliminotris(dimethylamino)tantalum complex was obtained in a second crystallization apparatus. t BuN=Ta(NMe2)3.

[0229] In this embodiment, the molar ratio of Me3SiNMe2 to TaCl5 is 4:1; the mass ratio of TaCl5 to n-heptane is 1:4; and the mass ratio of TaCl5 to Me3SiNH2 is... t The molar ratio of Bu to other materials is 1:1.

[0230] Example 2-3

[0231] This embodiment provides a method for preparing an iminotris(dimethylamino)tantalum complex, the method comprising the following steps:

[0232] (1) Under nitrogen atmosphere, in a 1L reaction apparatus, 10.75g (0.030mol) TaCl5 and 14.8g (0.126mol) Me3SiNMe2 were reacted in 430g (628mL) of inert solvent n-heptane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNMe2 was heated and distilled to obtain a tetra(dimethylamino)tantalum chloride Ta(NMe2)4Cl solution.

[0233] The obtained tetra(dimethylamino)tantalum chloride Ta(NMe2)4Cl solution was subjected to vacuum distillation and sublimation in a sublimator to obtain tetra(dimethylamino)tantalum chloride in the first crystallization apparatus;

[0234] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0235] (2) Under a nitrogen atmosphere, the temperature was maintained at 60°C to prepare 4.80 g (0.033 mol) of trimethylsilyl tert-butylamine Me3SiNH. t Bu was added dropwise with continuous stirring during the addition process. After 2 hours of addition, ligand exchange was performed to obtain the product solution.

[0236] Ligand exchange was carried out under stirring conditions at a stirring speed of 100 rpm; the ligand exchange temperature was 60℃ for 2 h, followed by 80℃ for 2 h.

[0237] The resulting product solution was subjected to vacuum distillation and sublimation in a sublimator, and the tert-butyliminotris(dimethylamino)tantalum complex was obtained in a second crystallization apparatus. t BuN=Ta(NMe2)3.

[0238] In this embodiment, the molar ratio of Me3SiNMe2 to TaCl5 is 4.2:1; the mass ratio of TaCl5 to n-heptane is 1:40; and the mass ratio of TaCl5 to Me3SiNH2 is... t The molar ratio of Bu to other materials is 1:1.1.

[0239] Examples 2-4

[0240] This embodiment provides a method for preparing an iminotris(dimethylamino)tantalum complex, the method comprising the following steps:

[0241] (1) Under nitrogen atmosphere, in a 1L reaction apparatus, 35.8g (0.10mol) TaCl5 and 48.1g (0.41mol) Me3SiNMe2 reacted in 358g (523mL) of inert solvent n-heptane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNMe2 was heated and distilled to obtain a tetra(dimethylamino)tantalum chloride Ta(NMe2)4Cl solution.

[0242] The obtained tetra(dimethylamino)tantalum chloride Ta(NMe2)4Cl solution was subjected to vacuum distillation and sublimation in a sublimator to obtain tetra(dimethylamino)tantalum chloride in the first crystallization apparatus;

[0243] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0244] (2) Under a nitrogen atmosphere, the temperature was maintained at 60°C to prepare 13.9 g (0.106 mol) of trimethylsilylisopropylamine Me3SiNH. i Pr was added dropwise with continuous stirring during the addition process. After 2 hours of addition, ligand exchange was performed to obtain the product solution.

[0245] Ligand exchange was carried out under stirring conditions at a stirring speed of 100 rpm; the ligand exchange temperature was 60℃ for 2 h, followed by 80℃ for 2 h.

[0246] The resulting product solution was subjected to vacuum distillation and sublimation in a sublimator, and the isopropyliminotris(dimethylamino)tantalum complex was obtained in a second crystallization apparatus. i PrN=CpTa(NMe2)3.

[0247] In this embodiment, the molar ratio of Me3SiNMe2 to TaCl5 is 4.1:1; the mass ratio of TaCl5 to n-heptane is 1:10; and the mass ratio of TaCl5 to Me3SiNH2 is... i The molar ratio of Pr to feed is 1:1.06.

[0248] Examples 2-5

[0249] This embodiment provides a method for preparing an iminotris(methylethylamino)tantalum complex, the method comprising the following steps:

[0250] (1) Under nitrogen atmosphere, in a 1L reaction apparatus, 35.8g (0.10mol) TaCl5 and 53.8g (0.41mol) Me3SiNEtMe were reacted in 358g (509mL) of inert solvent n-octane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNEtMe was heated and distilled to obtain a tetra(methylethylamino)tantalum chloride Ta(NEtMe)4Cl solution.

[0251] The obtained tetra(methylethylamino)tantalum chloride Ta(NEtMe)4Cl solution was subjected to vacuum distillation and sublimation in a sublimator to obtain tetra(methylethylamino)tantalum chloride in a first crystallization apparatus.

[0252] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0253] (2) Under a nitrogen atmosphere, the temperature was maintained at 60°C to prepare 16.9 g (0.106 mol) of trimethylsilyl tert-amylamine Me3SiNH. t Am was added dropwise with continuous stirring during the addition process. After 2 hours of addition, ligand exchange was performed to obtain the product solution.

[0254] Ligand exchange was carried out under stirring conditions at a stirring speed of 100 rpm; the ligand exchange temperature was 60℃ for 2 h, followed by 80℃ for 2 h.

[0255] The resulting product solution was subjected to vacuum distillation and sublimation in a sublimator, and the tert-amyliminotris(methylethylamino)tantalum complex was obtained in a second crystallization apparatus. t AmN=Ta(NEtMe)3.

[0256] In this embodiment, the molar ratio of Me3SiNEtMe to TaCl5 is 4.1:1; the mass ratio of TaCl5 to n-octane is 1:10; and the mass ratio of TaCl5 to Me3SiNH is... t The molar ratio of Am to other materials is 1:1.06.

[0257] Examples 2-6

[0258] This embodiment provides a method for preparing an iminotris(methylethylamino)tantalum complex, the method comprising the following steps:

[0259] (1) Under nitrogen atmosphere, in a 1L reaction apparatus, 35.8g (0.10mol) TaCl5 and 53.8g (0.41mol) Me3SiNEtMe were reacted in 358g (509mL) of inert solvent n-octane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNEtMe was heated and distilled to obtain a tetra(methylethylamino)tantalum chloride Ta(NEtMe)4Cl solution.

[0260] The obtained tetra(methylethylamino)tantalum chloride Ta(NEtMe)4Cl solution was subjected to vacuum distillation and sublimation in a sublimator to obtain tetra(methylethylamino)tantalum chloride in a first crystallization apparatus.

[0261] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0262] (2) Under nitrogen atmosphere, the temperature was maintained at 60°C for the dropwise addition of 16.7 g (0.106 mol) of trimethylsilylcyclopentylamine Me3SiNHCp. The mixture was stirred continuously during the dropwise addition. After 2 h of dropwise addition, ligand exchange was performed to obtain the product solution.

[0263] Ligand exchange was carried out under stirring conditions at a stirring speed of 100 rpm; the ligand exchange temperature was 60℃ for 2 h, followed by 80℃ for 2 h.

[0264] The resulting product solution was subjected to vacuum distillation and sublimation in a sublimator, and the cyclopentyliminotris(dimethylethylamino)tantalum complex CpN=Ta(NEtMe)3 was obtained in a second crystallization apparatus.

[0265] In this embodiment, the molar ratio of Me3SiNEtMe to TaCl5 is 4.1:1; the mass ratio of TaCl5 to n-octane is 1:10; and the molar ratio of TaCl5 to Me3SiNHCp is 1:1.06.

[0266] Examples 2-7

[0267] This embodiment provides a method for preparing an iminotris(diethylamino)tantalum complex, the method comprising the following steps:

[0268] (1) Under nitrogen atmosphere, in a 1L reaction apparatus, 35.8g (0.10mol) TaCl5 and 59.6g (0.41mol) Me3SiNEt2 were reacted in 358g (497mL) of inert solvent n-nonane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNEt2 was heated and distilled to obtain a tetra(diethylamino)tantalum chloride solution.

[0269] The obtained tetra(diethylamino)tantalum chloride Ta(NEt2)4Cl solution was subjected to vacuum distillation and sublimation in a sublimator to obtain tetra(diethylamino)tantalum chloride in a first crystallization apparatus.

[0270] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0271] (2) Under nitrogen atmosphere, the temperature was maintained at 60°C for the dropwise addition of 18.2 g (0.106 mol) of trimethylsilylcyclohexylamine Me3SiNHCy. The mixture was stirred continuously during the dropwise addition. After 2 h of dropwise addition, ligand exchange was performed to obtain the product solution.

[0272] Ligand exchange was carried out under stirring conditions at a stirring speed of 100 rpm; the ligand exchange temperature was 60℃ for 2 h, followed by 80℃ for 2 h.

[0273] The resulting product solution was subjected to vacuum distillation and sublimation in a sublimator, and the cyclohexyliminotris(diethylamino)tantalum complex CyN=Ta(NEt2)3 was obtained in a second crystallization apparatus.

[0274] In this embodiment, the molar ratio of Me3SiNEt2 to TaCl5 is 4.1:1; the mass ratio of TaCl5 to n-nonane is 1:10; and the molar ratio of TaCl5 to Me3SiNHCy is 1:1.06.

[0275] Examples 2-8

[0276] This embodiment provides a method for preparing an iminotris(dimethylamino)tantalum complex, the method comprising the following steps:

[0277] (1) Under nitrogen atmosphere, in a 1L reaction apparatus, 35.8g (0.130mol) TaF5 and 62.5g (0.533mol) Me3SiNMe2 were reacted in 358g (543mL) of inert solvent n-hexane. After the byproduct Me3SiF no longer evaporated, the unreacted Me3SiNMe2 was heated and distilled to obtain a tetra(dimethylamino)tantalum fluoride solution.

[0278] The obtained tetra(dimethylamino)tantalum fluoride Ta(NMe2)4F solution was subjected to vacuum distillation and sublimation in a sublimator to obtain tetra(dimethylamino)tantalum fluoride in a first crystallization apparatus.

[0279] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 30℃ and the reaction time was 6 h.

[0280] (2) Under a nitrogen atmosphere, the temperature was maintained at 30°C to prepare 20.1 g (0.138 mol) of trimethylsilyl tert-butylamine Me3SiNH. t Bu was added dropwise with continuous stirring during the addition process. After 2 hours of addition, ligand exchange was performed to obtain the product solution.

[0281] Ligand exchange was carried out under stirring conditions at a stirring speed of 100 rpm; the ligand exchange temperature was 30℃ for 2 h, followed by 50℃ for 2 h.

[0282] The resulting product solution was subjected to vacuum distillation and sublimation in a sublimator, and the tert-butyliminotris(dimethylamino)tantalum complex was obtained in a second crystallization apparatus.

[0283] In this embodiment, the molar ratio of Me3SiNMe2 to TaF5 is 4.1:1; the mass ratio of TaF5 to n-hexane is 1:10; and the mass ratio of TaF5 to Me3SiNH2 is... t The molar ratio of Bu to feed is 1:1.06.

[0284] Examples 2-9

[0285] This embodiment provides a method for preparing an iminotris(dimethylamino)tantalum complex, the method comprising the following steps:

[0286] (1) Under nitrogen atmosphere, in a 1L reaction apparatus, 35.8g (61.7mmol) TaBr5 and 29.7g (0.253mol) Me3SiNMe2 were reacted in 358g (411mL) of inert solvent toluene. The unreacted Me3SiNMe2 and the generated byproduct Me3SiBr were distilled by heating to obtain a tetra(dimethylamino)tantalum bromide solution.

[0287] The obtained tetra(dimethylamino)tantalum bromide Ta(NMe2)4Br solution was subjected to vacuum distillation and sublimation in a sublimator to obtain tetra(dimethylamino)tantalum bromide in the first crystallization apparatus.

[0288] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 80℃ and the reaction time was 6 h.

[0289] (2) Under a nitrogen atmosphere, the temperature was maintained at 80°C to carry out the reaction of 9.50 g (65.4 mmol) of trimethylsilyl tert-butylamine Me3SiNH. t Bu was added dropwise with continuous stirring during the addition process. After 2 hours of addition, ligand exchange was performed to obtain the product solution.

[0290] Ligand exchange was carried out under stirring conditions at a stirring speed of 100 rpm; the ligand exchange temperature was 80℃ for 2 h, followed by 100℃ for 2 h.

[0291] The resulting product solution was subjected to vacuum distillation and sublimation in a sublimator, and the tert-butyliminotris(dimethylamino)tantalum complex was obtained in a second crystallization apparatus.

[0292] In this embodiment, the molar ratio of Me3SiNMe2 to TaBr5 is 4.1:1; the mass ratio of TaBr5 to toluene is 1:10; and the mass ratio of TaBr5 to Me3SiNH2 is... t The molar ratio of Bu to feed is 1:1.06.

[0293] Example 2-10

[0294] This embodiment provides a method for preparing an iminotris(dimethylamino)tantalum complex, except for modifying the trimethylsilyl tert-butylamine Me3SiNH t The amount of Bu fed allows tantalum chloride to react with Me3SiNH. t Except for the molar ratio of Bu to its feed, which is 1:0.95, all other aspects are the same as in Example 2-1.

[0295] Example 2-11

[0296] This embodiment provides a method for preparing tris(dimethylamino)tantalum complexes, except for modifying trimethylsilyl tert-butylamine Me3SiNH t The amount of Bu fed allows tantalum chloride to react with Me3SiNH. t Except for the molar ratio of Bu to its feed, which is 1:1.15, all other aspects are the same as in Example 2-1.

[0297] The mass, yield calculated based on the tantalum halide feed, and HPLC purity of the tris(dialkylamino)tantalum complexes prepared in the above examples were determined, and the results are shown in Table 2.

[0298] Table 2

[0299] Example 2-1 33.4 87 99.99 Example 2-2 61.5 80 99.57 Example 2-3 9.9 86 99.99 Examples 2-4 31.5 85 99.99 Examples 2-5 37.4 85 99.96 Examples 2-6 37.7 86 99.94 Examples 2-7 40.1 81 99.90 Examples 2-8 44.5 89 99.99 Examples 2-9 18.0 76 99.5 Example 2-10 25.0 65 99.99 Example 2-11 23.8 62 99.99

[0300] Example 3-1

[0301] This embodiment provides a method for preparing penta(dimethylamino)niobium, the method comprising the following steps:

[0302] Under nitrogen atmosphere, in a 1L reaction apparatus, 32.4g (0.12mol) of NbCl5 and 105.5g (0.90mol) of Me3SiNMe2 were reacted in 324g (474mL) of inert solvent n-heptane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNMe2 was heated and distilled to obtain a pentapentan(dimethylamino)niobium Nb(NMe2)5 solution.

[0303] The obtained penta(dimethylamino)niobium Nb(NMe2)5 solution was subjected to vacuum distillation and sublimation in a sublimator to obtain penta(dimethylamino)niobium in a first crystallization apparatus.

[0304] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0305] In this embodiment, the molar ratio of Me3SiNMe2 to NbCl5 is 7.5:1; the mass ratio of NbCl5 to n-heptane is 1:10.

[0306] Example 3-2

[0307] This embodiment provides a method for preparing penta(methylethylamino)niobium, which is the same as in Example 3-1 except that the molar amount of Me3SiNMe2 is replaced with Me3SiNEtMe and the mass of n-heptane is replaced with n-octane.

[0308] Example 3-3

[0309] This embodiment provides a method for preparing penta(diethylamino)niobium, which is the same as in Example 3-1 except that the molar amount of Me3SiNMe2 is replaced with Me3SiNEt2 and the mass of n-heptane is replaced with n-nonane.

[0310] Examples 3-4

[0311] This embodiment provides a method for preparing penta(dimethylamino)niobium, the method comprising the following steps:

[0312] Under nitrogen atmosphere, in a 1L reaction apparatus, 32.4g (0.172mol) of NbF5 and 151.3g (1.29mol) of Me3SiNMe2 were reacted in 324g (492mL) of inert solvent n-hexane. After the byproduct Me3SiF stopped distilling out, the unreacted Me3SiNMe2 was heated and distilled to obtain a pentapentan(dimethylamino)niobium Nb(NMe2)5 solution.

[0313] The obtained penta(dimethylamino)niobium Nb(NMe2)5 solution was subjected to vacuum distillation and sublimation in a sublimator to obtain penta(dimethylamino)niobium in a first crystallization apparatus.

[0314] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0315] In this embodiment, the molar ratio of Me3SiNMe2 to NbF5 is 7.5:1; the mass ratio of NbF5 to n-hexane is 1:10.

[0316] Examples 3-5

[0317] This embodiment provides a method for preparing penta(dimethylamino)niobium, the method comprising the following steps:

[0318] Under nitrogen atmosphere, in a 1L reaction apparatus, 32.4g (65.8mmol) NbBr5 and 57.9g (0.494mol) Me3SiNMe2 were reacted in 324g (372mL) of inert solvent toluene. The unreacted Me3SiNMe2 and the generated byproduct Me3SiBr were distilled by heating to obtain a pentapentan(dimethylamino)niobium Nb(NMe2)5 solution.

[0319] The obtained penta(dimethylamino)niobium Nb(NMe2)5 solution was subjected to vacuum distillation and sublimation in a sublimator, and penta(dimethylamino)niobium was obtained in the first fractionation device.

[0320] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 80℃ and the reaction time was 6 h.

[0321] In this embodiment, the molar ratio of Me3SiNMe2 to NbBr5 is 7.5:1; the mass ratio of NbBr5 to toluene is 1:10.

[0322] The mass of the dialkylamino metal halides prepared in the above examples, the yield calculated based on the niobium halide feed, and the HPLC purity were determined, and the results are shown in Table 3.

[0323] Table 3

[0324] Example 3-1 32.0 85 99.99 Example 3-2 38.6 84 99.99 Example 3-3 44.1 81 99.97 Examples 3-4 46.9 87 99.99 Examples 3-5 14.6 71 99.91

[0325] Example 4-1

[0326] This embodiment provides a method for preparing an iminotris(dimethylamino)niobium complex, the method comprising the following steps:

[0327] (1) Under nitrogen atmosphere, in a 1L reaction apparatus, 32.4g (0.12mol) NbCl5 and 57.7g (0.492mol) Me3SiNMe2 were reacted in 324g (474mL) of inert solvent n-heptane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNMe2 was heated and distilled to obtain a tetra(dimethylamino)niobium chloride Nb(NMe2)4Cl solution.

[0328] The obtained tetra(dimethylamino)niobium chloride Nb(NMe2)4Cl solution was subjected to vacuum distillation and sublimation in a sublimator to obtain tetra(dimethylamino)niobium chloride in the first crystallization apparatus.

[0329] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0330] (2) Under a nitrogen atmosphere, the temperature was maintained at 60°C to prepare 18.5 g (0.127 mol) of trimethylsilyl tert-butylamine Me3SiNH. t Bu was added dropwise with continuous stirring during the addition process. After 2 hours of addition, ligand exchange was performed to obtain the product solution.

[0331] Ligand exchange was carried out under stirring conditions at a stirring speed of 100 rpm; the ligand exchange temperature was 60℃ for 2 h, followed by 80℃ for 2 h.

[0332] The resulting product solution was subjected to vacuum distillation and sublimation in a sublimator, and the tert-butyliminotris(dimethylamino)niobium complex was obtained in a second crystallization apparatus. t BuN=Nb(NMe2)3.

[0333] In this embodiment, the molar ratio of Me3SiNMe2 to NbCl5 is 4.1:1; the mass ratio of NbCl5 to n-heptane is 1:10; and the mass ratio of NbCl5 to Me3SiNH2 is... t The molar ratio of Bu to feed is 1:1.06.

[0334] Example 4-2

[0335] This embodiment provides a method for preparing an iminotris(diethylamino)niobium complex, the method comprising the following steps:

[0336] (1) Under nitrogen atmosphere, in a 1L reaction apparatus, 32.4g (0.12mol) NbCl5 and 59.6g (0.41mol) Me3SiNEt2 were reacted in 324g (450mL) of inert solvent n-nonane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNEt2 was heated and distilled to obtain a tetra(diethylamino)niobium chloride solution.

[0337] The obtained tetra(diethylamino)niobium chloride Nb(NEt2)4Cl solution was subjected to vacuum distillation and sublimation in a sublimator to obtain tetra(diethylamino)niobium chloride in the first crystallization apparatus.

[0338] The reaction was carried out under stirring conditions, with a stirring speed of 100 rpm; the reaction temperature was 60℃ and the reaction time was 6 h.

[0339] (2) Under nitrogen atmosphere, the temperature was maintained at 60°C for the dropwise addition of 21.8 g (0.127 mol) of trimethylsilylcyclohexylamine Me3SiNHCy. The mixture was stirred continuously during the dropwise addition. After 2 hours of dropwise addition, ligand exchange was performed to obtain the product solution.

[0340] Ligand exchange was carried out under stirring conditions at a stirring speed of 100 rpm; the ligand exchange temperature was 60℃ for 2 h, followed by 80℃ for 2 h.

[0341] The resulting product solution was subjected to vacuum distillation and sublimation in a sublimator, and the cyclohexyliminotris(diethylamino)niobium complex CyN=Nb(NEt2)3 was obtained in a second crystallization apparatus.

[0342] In this embodiment, the molar ratio of Me3SiNEt2 to NbCl5 is 4.1:1; the mass ratio of NbCl5 to n-nonane is 1:10; and the molar ratio of NbCl5 to Me3SiNHCy is 1:1.06.

[0343] The mass, yield calculated based on the niobium halide feed, and HPLC purity of the tris(dialkylamino)niobium complexes prepared in the above examples were determined, and the results are shown in Table 4.

[0344] Table 4

[0345] Example 4-1 28.4 80 99.99 Example 4-2 36.1 74 99.97

[0346] In summary, the preparation method and preparation apparatus provided by the present invention have the following advantages:

[0347] (1) The method for preparing dialkylamino metal halides provided by the present invention utilizes trimethylsilyl dialkylamine to dehalogenate the halides. The reaction is easy to control, the operation is simple, and no solid waste such as lithium halides that are difficult to separate is generated. The product obtained has high purity and is easy to realize industrial production.

[0348] (2) The method for preparing iminotris(dialkylamino) metal complexes provided by the present invention is to fully dehalogenate halides with trimethylsilyldialkylamine to prepare intermediate tetra(dialkylamino) halides, and then perform ligand exchange with trimethylsilylmonoalkylamine to prepare the product. This method is a solid-liquid reaction between halides and dehalogenating agents, which is different from the solid-solid reaction between lithium alkylamino and halides. It is easier to disperse evenly. Within the boiling point range allowed by the dehalogenating agent, the dehalogenation reaction can be carried out at a higher temperature and the reaction rate is faster. This method can avoid the metal impurities introduced by the impure n-butyllithium used in the lithium alkylamino technical route, and can also avoid the generation of solid wastes such as lithium salts that are not easy to separate later. It facilitates product purification and the obtained product is easy to meet the purity requirements of precursor materials in integrated circuit manufacturing.

[0349] Trimethylsilyldialkylamine serves as a reactant, acting as a dehalogenating agent for halides, a donor of dialkylamino ligands, and a chemical dehydrating agent. Adding a slight excess of trimethylsilyldialkylamine during the reaction ensures complete dehalogenation of the halides and removes trace amounts of moisture remaining in the reaction apparatus and materials, thus facilitating product formation. Using trimethylsilyl monoalkylamine as a primary amine donor allows for a faster reaction rate at higher temperatures within the permissible boiling point range.

[0350] (3) The reaction apparatus for preparing high-purity dialkylamino metal halides and iminotris(dialkylamino) metal complexes provided by the present invention adopts the technical route of trimethylsilyldialkylamine, which does not require strict stoichiometric ratio of n-butyllithium or dialkylaminolithium as the technical route of dialkylaminolithium. The reaction conditions are easy to control. The reaction unit and the purification unit are used in combination in the apparatus. In addition to purifying the product, the by-products, unreacted trimethylsilyldialkylamine and solvent can also be recovered. At the same time, low-boiling-point dialkylamine and trimethylhalosilane are collected for regenerating trimethylsilyldialkylamine.

[0351] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for preparing an iminotris(dialkylamino) metal complex, characterized in that, The preparation method includes the following steps: (1) Under protective atmosphere conditions, in an inert solvent, the halide MX5 reacts with trimethylsilyldialkylamine Me3SiNR 1 R 2 The reaction yields tetra(dialkylamino)halides M(NR) 1 R 2 The reaction equation for the 4X solution is as follows: MX5 + Me3SiNR 1 R 2 → M(NR 1 R 2 )4X + Me3SiX; (2) Under a protective atmosphere, trimethylsilyl monoalkylamine Me3SiNHR3 reacts with the tetra(dialkylamino)halide M(NR) obtained in step (1). 1 R 2 The ligand exchange was performed using a 4X solution, and the product solution was purified to obtain the iminotris(dialkylamino)metal complex R. 3 N=M(NR 1 R 2 3. The reaction formula is as follows: M(NR 1 R 2 )4X + Me3SiNHR 3 → R 3 N=M(NR 1 R 2 )3 + Me3SiX + HNR 1 R 2 ; M is a fifth subgroup element; The halide MX5 is MF5 or MCl5; the mass ratio of the halide MX5 to the inert solvent in step (1) is 1:4 to 1:40; The R 1 R 2 With R 3 Each is independently hydrogen-based and / or alkyl-based, where N is an amino nitrogen and Me is a methyl group.

2. The preparation method according to claim 1, characterized in that, The R 1 With R 2 Each is independently methyl and / or ethyl.

3. The preparation method according to claim 1, characterized in that, The R 3 It is any one or a combination of at least two of tert-butyl, tert-pentyl, isopropyl, cyclohexyl, or cyclopentyl.

4. The preparation method according to claim 1, characterized in that, The trimethylsilyldialkylamine Me3SiNR 1 R 2 The molar ratio of the feed to halide MX5 is 4:1 to 4.2:

1.

5. The preparation method according to claim 1, characterized in that, The reaction temperature in step (1) is lower than that of trimethylsilyldialkylamine Me3SiNR. 1 R 2 The boiling point of .

6. The preparation method according to claim 1, characterized in that, The reaction in step (1) is carried out at a temperature higher than the boiling point of trimethylsilane Me3SiX.

7. The preparation method according to claim 1, characterized in that, The reaction temperature in step (1) is from 0°C to 150°C.

8. The preparation method according to claim 7, characterized in that, The reaction temperature in step (1) is 20°C to 120°C.

9. The preparation method according to claim 1, characterized in that, The reaction time in step (1) is 3 to 30 hours.

10. The preparation method according to claim 1, characterized in that, The halide MX5 and trimethylsilyl monoalkylamine Me3SiNHR 3 The molar ratio of the feed is 1:1 to 1:1.

1.

11. The preparation method according to claim 1, characterized in that, The ligand exchange temperature in step (2) is lower than that of trimethylsilyl monoalkylamine Me3SiNHR. 3 The boiling point of .

12. The preparation method according to claim 11, characterized in that, The ligand exchange temperature in step (2) is higher than that of trimethylhalosilane Me3SiX and dialkylamine HNR. 1 R 2 The boiling point of .

13. The preparation method according to claim 1, characterized in that, The temperature for ligand exchange in step (2) is from -20°C to 150°C.

14. The preparation method according to claim 13, characterized in that, The temperature for ligand exchange in step (2) is 20°C to 120°C.

15. The preparation method according to claim 1, characterized in that, The ligand exchange time in step (2) is 2 to 20 hours.

16. The preparation method according to claim 1, characterized in that, The inert solvent in step (1) is a hydrocarbon solvent that does not participate in the reaction.

17. The preparation method according to claim 16, characterized in that, The inert solvent in step (1) is a hydrocarbon solvent with a boiling point below 150°C.

18. The preparation method according to claim 17, characterized in that, The inert solvent in step (1) is Me3SiNR, which has a boiling point higher than that of trimethylsilyldialkylamine. 1 R 2 Hydrocarbon solvents with a boiling point above 10°C.

19. The preparation method according to claim 18, characterized in that, The inert solvent in step (1) is any one or a combination of at least two of n-heptane, n-octane, toluene, o-xylene or m-xylene.

20. The preparation method according to claim 1, characterized in that, The protective atmosphere is provided by an inert gas, which is nitrogen.

21. The preparation method according to claim 1, characterized in that, The reaction described in step (1) and / or the ligand exchange described in step (2) are carried out under stirring conditions.

22. The preparation method according to claim 21, characterized in that, The stirring speed under the specified stirring conditions is 30 rpm to 150 rpm.

23. The preparation method according to claim 1, characterized in that, The apparatus system used to prepare the iminotris(dialkylamino) metal complex includes a reaction unit, a pretreatment unit, a filtration unit, a purification unit, and a nitrogen supply unit. The reaction unit includes a reaction apparatus, a trimethylsilyl dialkylamine supply device, a halide supply device, and a trimethylsilyl monoalkylamine supply device; the trimethylsilyl dialkylamine supply device, the halide supply device, and the trimethylsilyl monoalkylamine supply device are each independently connected to the reaction apparatus through a feed pipeline. The nitrogen supply pipeline of the nitrogen supply unit is connected to the feed pipeline of the trimethylsilyldialkylamine supply device and the feed pipeline of the halide supply device, respectively. The pretreatment unit includes a condensation device and a first vacuum generator connected in sequence; the condensation device includes at least one condenser connected in series, and the bottom outlet of the last condenser is connected to a light phase storage tank; the first vacuum generator is used to control the vacuum level of the condensation device. The purification unit includes a sublimator, a fractionation device, a second vacuum generator, a first crystallization device, a second crystallization device, and a third vacuum generator; the light phase outlet of the sublimator is connected to the fractionation device; the second vacuum generator is used to control the vacuum level of the fractionation device; the sublimator is also connected to the first crystallization device and the second crystallization device; the third vacuum generator is used to control the vacuum level of the first crystallization device and the second crystallization device. The discharge port of the reaction device and the inlet of the sublimator are each independently connected to the filtration unit.

24. The preparation method according to claim 23, characterized in that, The fractionation apparatus includes a distillation column and a heavy phase storage tank; The light phase outlet of the sublimator is connected to the feed inlet of the distillation column; The heavy phase outlet of the distillation column is connected to the heavy phase storage tank.

25. The preparation method according to claim 23, characterized in that, The filtration unit includes at least two filters connected in parallel; the outlet of the reaction device and the inlet of the sublimator are respectively connected to the two ends of the filters.

26. The preparation method according to claim 25, characterized in that, The connecting pipes between the filter and the reaction device, and between the filter and the sublimator, are respectively connected to the nitrogen supply pipes of the nitrogen supply unit.

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