Process and apparatus system for the preparation of dialkylamino metal halides, diimino bis(dialkylamino) metal complexes

Abstract

The application provides a preparation method and device system of dialkylamino metal halide and diimino bis(dialkylamino) metal complex, and the device system corresponds to the preparation method. The preparation method promotes the reaction of the formation of the favorable product, reduces the occurrence of the side reaction, avoids the defects of the introduction of metal impurities by using n-butyl lithium, avoids the generation of lithium salt and other components which are inconvenient for subsequent separation, and facilitates the purification of the product. Moreover, the dialkylamino metal halide and diimino bis(dialkylamino) metal complex prepared by the application meet the purity requirements of the precursor material in integrated circuit manufacturing.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of semiconductor precursor material production, and relates to a preparation method and device system of a precursor material, in particular to a preparation method and device system of a dialkylamino metal halide and a diimino bis(dialkylamino) metal complex. BACKGROUND

[0002] Nitrides of the sixth transition group elements have the advantages of good conductivity, high melting point, high activation energy of lattice and grain boundary diffusion, and good thermal stability, and can be used as a barrier layer for preventing copper diffusion in semiconductor microcircuit. At present, copper metal wiring is widely used instead of aluminum metal wiring, and in order to maximize the inhibition of internal delamination and electron migration that may occur during annealing in copper wiring technology, a material capable of effectively preventing copper diffusion and having good adhesion to copper must be used to form a diffusion prevention film.

[0003] Taking tungsten in the sixth transition group elements as an example, tungsten nitride can be used as a good barrier layer material, in addition, tungsten nitride can also be used as an electrode of a thin film capacitor and a field effect transistor, and a contact of a dynamic random access memory (DRAM) structure, and a molybdenum nitride layer can be used together with an alternating layer of silicon to produce a mirror surface for X-rays.

[0004] At present, tungsten nitride films are mainly prepared by ALD deposition of tungsten hexafluoride (WF6) and ammonia (NH3), in which WF6 and NH3 are used as tungsten precursors and nitrogen sources respectively, and the chemical reaction formula of the reaction is as follows:

[0005] 2WF6+2NH3+3H2→2WN+12HF

[0006] This process has good step coverage, but WF6 and / or its reaction by-products HF can erode substrates made of Si or SiO2; and the generated unnecessary by-product ammonium fluoride particles can cause defects in semiconductor products. In addition, this process leaves fluorine residues on the surface of tungsten nitride, which can hinder the CVD adhesion of copper, and the loss of such adhesion can cause a serious reduction in the yield of finished products in production or safety problems during the operation of semiconductor devices.

[0007] Hexakis(dimethylamino)tungsten (W(NMe2)6), hexakis(diethylamino)tungsten (W(NEt2)6) and di-tert-butyliminobis(dimethylamino)tungsten ((BuN=)2W(NMe2)2) are metal complex materials for tungsten nitride film deposition. t BuN=)2W(NMe2)2) are metal complex materials for tungsten nitride film deposition.

[0008] The synthesis of W(NR 1 R 2 )6 of hexakis(dialkylamino)tungsten is mostly carried out by using lithium dialkylamide LiNR 1 R2 and a preparation process of tungsten halide WX6 as raw material, the chemical formula of the reaction is:

[0009] WX6+ LiNR 1 R 2 → W(NR 1 R 2 )6+ LiX

[0010] For example, using hexakis(dimethylamino)tungsten W(NMe2)6, the mixture of unreacted WCl6 and LiNMe2 will explode or have a highly exothermic reaction during separation, increasing the safety risk of the process. In addition, n-butyllithium is inevitably used in the reaction, and the reaction conditions are relatively harsh. The use of such metal reagents can easily introduce metal impurities that are difficult to separate, affecting the purity of the final product; and the generation of lithium halide and other solid waste during the reaction process also increases the difficulty of separation. The reaction between solid-phase tungsten halide and lithium dialkylamide is highly dependent on the dispersion effect of the solvent medium: too low a solvent ratio will affect the dispersion of tungsten halide, slowing down the reaction rate; too high a solvent ratio will have a good dispersion effect on tungsten halide, but the synthesis efficiency of a single batch will be low. To promote the reaction, pyridine and ether solvents (such as tetrahydrofuran and diethyl ether) are introduced to assist dispersion, which can easily obtain complexes of tungsten metal with pyridine and ether, affecting the subsequent separation and purification.

[0011] The synthesis of diimino bis(dialkylamino) tungsten (R 3 N=)2W(NR 1 R 2 )2 usually adopts the following two methods in specific implementation:

[0012] The first method first uses LiNR 1 R 2 and WX6 to prepare an intermediate product hexakis(dialkylamino)tungsten W(NR 1 R 2 )6, and then performs ligand exchange with 2 times the molar amount of primary amine R 3 NH2 to prepare (R 3 N=)2W(NR 1 R 2 )2:

[0013] WX6+ LiNR 1 R 2 → W(NR 1 R 2 )6+ LiX

[0014] W(NR 1 R 2 )6+ 2R 3 NH2→ (R 3 N=)2W(NR 1 R2 )2+4HNR 1 R 2 ;

[0015] The second way is to use WX6 and 4 times of molar amount of LiNR 1 R 2 , 2 times of molar amount of LiNHR 3 The "one pot" reaction to prepare (R 3 N=)2W(NR 1 R 2 )2:

[0016] WX6+4LiNR 1 R 2 +2LiNHR3→(R 3 N=)2W(NR 1 R 2 )2+6LiX+2HNR 1 R 2

[0017] The ligand exchange reaction between the primary amino R 3 NH2 and W(NR 1 R 2 )5 in the first way is more suitable for aromatic primary amino, and is not suitable for aliphatic primary amino; the "one pot" reaction in the second way is simple in operation steps, but involves the solid phase reaction of WX6 and LiNR 1 R 2 , LiNHR 3 The overall yield of the solid phase reaction of lithium amide salt is not high. As in the preparation of W(NR 1 R 2 )6, the n-butyllithium is inevitably used in both methods, the conditions are relatively harsh, and metal impurities are easily introduced, affecting the purity of the final product; the solid waste such as lithium halide generated in the reaction process increases the difficulty of separation. The reaction between solid phase tungsten halide and lithium amide is highly dependent on the dispersion effect of the solvent medium.

[0018] Therefore, in order to meet the purity requirements of precursor materials in the integrated circuit manufacturing process, a preparation method and device system of dialkylamino metal halide and diimino bis(dialkylamino) metal complex are needed, which are easy to control, simple to separate, convenient to operate and suitable for industrial production. SUMMARY

[0019] In view of the deficiencies of the prior art, the present application aims to provide a preparation method and device system of dialkylamino metal halide and diimino bis(dialkylamino) metal complex, wherein the device system corresponds to the preparation method, the preparation method can reduce the occurrence of side reactions, avoids the defects of introducing metal impurities by using n-butyl lithium, and avoids the defects of producing lithium salt and other subsequent components which are not convenient to separate; moreover, the dialkylamino metal halide and diimino bis(dialkylamino) metal complex prepared by the present application can meet the purity requirements of precursor materials in the integrated circuit manufacturing process.

[0020] To achieve the above object, the present application adopts the following technical solutions:

[0021] In a first aspect, the present application provides a preparation method of dialkylamino metal halide, which comprises the following steps:

[0022] Under the condition of protective atmosphere, halide MX6 and trimethylsilyl dialkylamine Me3SiNR 1 R 2 react to obtain dialkylamino metal halide M(NR 1 R 2 ) 6-n X n solution, and the reaction formula is as follows:

[0023] MX6+Me3SiNR 1 R 2 →M(NR 1 R 2 ) 6-n X n +Me3SiX;

[0024] The M is a sixth subgroup element;

[0025] The X is halogen;

[0026] The n is 0-2;

[0027] The R 1 and R 2 are independently alkyl, the N is amino nitrogen, and the Me is methyl.

[0028] In the preparation method of dialkylamino metal halide provided by the present application, trimethylsilyl dialkylamine Me3SiNR 1 R 2 reacts with halide MX6 under the condition of protective atmosphere to obtain dialkylamino metal halide M(NR 2As a reactant, on one hand, a dialkylamino ligand is provided, and on the other hand, it can act as a dehalogenating agent for halide MX6. The dehalogenated product Me3SiX escapes from the reaction system in a gaseous form, which is favorable for the reaction to proceed in a positive direction. Therefore, the boiling point of Me3SiX is particularly important for promoting the positive direction of the entire reaction. According to the generation rate of Me3SiX, in order to make the reaction proceed in a positive direction, the trimethylsilyl dialkylamine Me3SiNR 1 R 2 may be added in batches or in a dropwise manner.

[0029] The B in the present application is a sixth subgroup element, including tungsten and / or molybdenum.

[0030] Preferably, the preparation method further comprises purifying the obtained dialkylamino metal halide M(NR 1 R 2 ) 6-n X n solution.

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

[0032] For example, when the trimethylsilyl dialkylamine Me3SiNR 1 R 2 is Me3SiNMe2 (boiling point 84°C), the boiling point of the escaping trimethylsilyl halide is below 84°C, which is favorable for the reaction to proceed in a positive direction. In this case, the halide is preferably MF6 and / or MCl6; when the trimethylsilyl dialkylamine Me3SiNR 1 R 2 is Me3SiNEt2 (Et is ethyl, boiling point 125°C to 126°C), the boiling point of the escaping trimethylsilyl halide is below 125°C, which is favorable for the reaction to proceed in a positive direction. In this case, the halide is preferably MF6 and / or MCl6, considering the boiling point of the halide and the content of the metal element in the halide.

[0033] Therefore, the halide MX6 is preferably MF6 and / or MCl6.

[0034] Preferably, the R 1 is the same as R2 each independently is methyl and / or ethyl.

[0035] Correspondingly, the trimethylsilyl dialkylamine Me3SiNR 1 R 2 is preferably any one of trimethylsilyl dimethylamine, trimethylsilyl diethylamine or trimethylsilyl methylethylamine or a combination of at least two thereof.

[0036] In the present application, the halide MX6and the trimethylsilyl dialkylamine Me3SiNR 1 R 2 react in an inert solvent to obtain a dialkylamino metal halide M(NR 1 R 2 ) 6-n X n solution, wherein n is 0 to 2, for example, can be 0, 1 or 2, but is not limited to the listed values, and other values not listed in the value range are also applicable. As a preferred technical solution, when n is 0, the trimethylsilyl dialkylamine Me3SiNR 1 R 2 is fed with a molar ratio of the halide MX6≥ 6:1. In order to ensure the generation efficiency of the product, the trimethylsilyl dialkylamine Me3SiNR 1 R 2 is fed with a molar ratio of the halide MX6of 6:1 to 14:1, for example, can be 6:1, 8:1, 10:1, 12:1 or 14:1, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0037] In the present application, the trimethylsilyl dialkylamine Me3SiNR 1 R 2 is fed with a molar ratio of the halide MX6of 6:1 to 14:1, which can ensure that MX6is completely converted into M(NR 1 R 2 )6, and reduce the generation of partially dehalogenated metal complexes.

[0038] Preferably, the halide MX6is fed with an inert solvent in a mass ratio of 1:4 to 1:40, for example, 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, and other values not listed in the value range are also applicable.

[0039] The inert solvent in the present application plays a role in dispersing and dissolving MX6and Me3SiNR 1 R 2 .

[0040] Preferably, the inert solvent comprises a hydrocarbon solvent that does not participate in the reaction.

[0041] The boiling point of the inert solvent used in the present application is higher than that of the trimethylsilyl halide Me3SiX, so as to avoid excessive removal of the inert solvent while removing Me3SiX; further, in order to reduce the evaporation of the solvent during purification, the boiling point of the inert solvent is preferably 10°C higher than that of Me3SiNR 1 R 2 ; and in order to facilitate the removal of the solvent after the reaction, the boiling point of the inert solvent is required to be no more than 150°C. Further preferably, the inert solvent is a hydrocarbon solvent with a boiling point of 60°C to 150°C, for example, it can be 60°C, 70°C, 80°C, 90°C, 100°C, 120°C or 150°C, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0042] Preferably, the inert solvent comprises any one or a combination of at least two of 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 mesitylene.

[0043] The xylene used in the present application comprises any one or a combination of at least two of p-xylene, m-xylene or o-xylene, and a typical but non-limiting combination includes a combination of p-xylene and m-xylene, a combination of m-xylene and o-xylene, a combination of p-xylene and o-xylene, or a combination of p-xylene, m-xylene and o-xylene.

[0044] The mesitylene used in the present application comprises any one or a combination of at least two of mestiylene, pseudomesitylene or durene, and a typical but non-limiting combination includes a combination of mestiylene and pseudomesitylene, a combination of pseudomesitylene and durene, a combination of mestiylene and durene, or a combination of mestiylene, pseudomesitylene and durene.

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

[0046] The reaction temperature in the first aspect of the present application is preferably lower than the boiling point of the trimethylsilyl dialkylamine Me3SiNR 1 R 2 , and higher than the boiling point of the trimethylsilyl halide Me3SiX. In order to reduce the precipitation of Me3SiNR 1 R 2 in the inert solvent, the reaction can proceed in the forward direction, and Me3SiNR 1 R 2The reaction temperature is preferably 0°C to 150°C, for example, it can be 0°C, 20°C, 30°C, 50°C, 60°C, 80°C, 100°C, 120°C or 150°C, but is not limited to the listed values, and other values not listed in the value range are also applicable, and preferably 20°C to 120°C.

[0047] For example, when the trimethylsilyl dialkylamine Me3SiNR 1 R 2 If MF6 is used as the metal source, the reaction temperature is preferably above 16°C and not more than 84°C; if MCl6 is used as the metal source, the reaction temperature is preferably above 57°C and not more than 84°C.

[0048] For example, when the trimethylsilyl dialkylamine Me3SiNR 1 R 2 If MF6 is used as the metal source, the reaction temperature is preferably above 16°C and not more than 84°C; if MCl6 is used as the metal source, the reaction temperature is preferably above 57°C and not more than 84°C.

[0049] The reaction time is preferably 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, and other values not listed in the value range are also applicable.

[0050] The reaction is preferably carried out under stirring.

[0051] The stirring speed of the stirring condition is preferably 30rpm to 150rpm, for example, it can be 30rpm, 40rpm, 50rpm, 60rpm, 80rpm, 100rpm, 120rpm or 150rpm, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0052] In a second aspect, the present application provides a device system for preparing the dialkylamine metal halide of the first aspect, which comprises a reaction unit, a pretreatment unit, a filtration unit, a purification unit and a nitrogen supply unit.

[0053] The reaction unit comprises a reaction device, a trimethylsilyl dialkylamine supply device and a halide supply device; the trimethylsilyl dialkylamine supply device and the halide supply device are respectively independently connected to the reaction device through a feeding pipeline;

[0054] The nitrogen supply pipeline of the nitrogen supply unit is connected with the feed pipeline of the trimethylsilyl dialkylamine supply device and the feed pipeline of the halide supply device, respectively;

[0055] The pre-treatment unit comprises a condenser and a first vacuum generating device connected in sequence; the condenser comprises at least one condenser connected in series, and the bottom discharge port of the last condenser is connected with a light phase storage tank; the first vacuum generating device is used for controlling the vacuum degree of the condenser;

[0056] The purification unit comprises a sublimator, a fractionating device, a second vacuum generating device, a first crystallization device and a third vacuum generating device; the light phase outlet of the sublimator is connected with the fractionating device; the second vacuum generating device is used for controlling the vacuum degree of the fractionating device; the sublimator is further connected with the first crystallization device; and the third vacuum generating device is used for controlling the vacuum degree of the first crystallization device.

[0057] The discharge port of the reaction device and the feed port of the sublimator are independently connected with the filtering unit, respectively.

[0058] Exemplarily, the first crystallization device comprises a first crystallizer and a first product storage tank connected below the first crystallizer.

[0059] When the device system provided by the second aspect is applied to prepare the dialkylamino metal halide M(NR 1 R 2 )6 of the first aspect, the following steps are performed:

[0060] (a) nitrogen is replaced in each unit and connecting pipeline involved in the preparation device system, and inert solvents, halides and trimethylsilyl dialkylamines are prepared according to the feeding amount;

[0061] (b) the inert solvents, halides and trimethylsilyl dialkylamines are mixed in the reaction device, and the temperature in the reaction device is controlled to make the reaction proceed;

[0062] (c) after the low-boiling-point components are removed by distillation in the reaction device, the product solution is filtered by the filtering unit, and then enters the sublimator;

[0063] (d) the temperature and pressure of the sublimator are controlled to perform vacuum distillation and sublimation, the inert solvents enter the fractionating device from the light phase outlet above the sublimator, and are collected in the heavy phase storage tank below the fractionating column; the dialkylamino metal halide enters the first crystallization device by vacuum sublimation, and is collected in the first product storage tank below the first crystallizer.

[0064] Exemplarily, the reaction device is provided with a stirring device; the stirring device includes but is not limited to an anchor stirring device or a frame stirring device.

[0065] Preferably, the first fractionating device comprises a rectifying column, a heavy phase tank; the heavy phase outlet of the rectifying column is connected with the heavy phase tank; the light phase outlet of the sublimer is connected with the feed inlet of the rectifying column; the first crystallizing device comprises a first crystallizer, a first product tank;

[0066] The inert solvent is recovered in the heavy phase tank, and the dialkylamino metal halide M(NR 1 R 2 )6 is obtained in the first product tank.

[0067] Preferably, the filtering unit comprises at least two filters connected in parallel; the outlet of the reaction device and the inlet of the sublimer are respectively connected with two ends of the filters.

[0068] Illustratively, the filters are normal pressure filters or pressurized filters.

[0069] Preferably, the connecting pipelines of the filters and the reaction device and the connecting pipelines of the filters and the sublimer are respectively connected with the nitrogen supply pipelines of the nitrogen supply unit.

[0070] In a third aspect, the present application provides a preparation method of a diimino bis(dialkylamino) metal complex, which comprises the following steps:

[0071] (1) under a protective atmosphere, halide MX6 reacts with trimethylsilyl dialkylamine Me3SiNR 1 R 2 in an inert solvent to obtain a solution of tetra(dialkylamino) halide, and the reaction formula is as follows:

[0072] MX6+4Me3SiNR 1 R 2 →M(NR 1 R 2 )4X2+4Me3SiX;

[0073] (2) under a protective atmosphere, trimethylsilyl monoalkylamine Me3SiNHR 3 reacts with the solution of tetra(dialkylamino) halide M(NR 1 R 2 )4X2 obtained in step (1) to exchange ligands, and the product solution is purified to obtain the diimino bis(dialkylamino) metal complex (R 3 N=)2M(NR 1 R 2 )2, and the reaction formula is as follows:

[0074] M(NR 1 R 2 )4X2+2Me3SiNHR 3→ (R 3 N = )2M (NR 1 R 2 )2+ 2Me3SiX + 2HNR 1 R 2 ;

[0075] said M is a sixth subgroup element;

[0076] said X is halogen;

[0077] said R 1 , R 2 and R 3 are independently alkyl, said N is amino nitrogen, and said Me is methyl.

[0078] The preparation method of the tris(dialkylamino)metal complex provided by the present application, wherein the trimethylsilyl dialkylamine Me3SiNR 1 R 2 serves as a dialkylamino ligand on one hand and as a dehalogenating agent for halide MX6 on the other hand. The dehalogenated product Me3SiX escapes from the reaction in gaseous form, which is conducive to the forward progress of the reaction, and therefore, the boiling point of Me3SiX is particularly important for promoting the forward progress of the entire reaction. According to the generation rate of Me3SiX, in order to make the reaction proceed in the forward direction, the trimethylsilyl dialkylamine Me3SiNR 1 R 2 may be added in batches or in a dropwise manner.

[0079] For example, the melting and boiling points of trimethylsilyl halides are as follows: the melting point of Me3SiF is -74°C, and the boiling point is 16°C; the melting point of Me3SiCl is -40°C, and the boiling point is 57°C; the melting point of Me3SiBr is -43°C, and the boiling point is 79°C; the melting point of Me3SiI is <0°C, and the boiling point is 106°C. When the byproduct Me3SiX escapes from the reaction in gaseous form, the trimethylsilyl dialkylamine serving as a dehalogenating agent is preferably retained in the system for continued reaction, and therefore, the boiling point of the trimethylsilyl dialkylamine Me3SiNR 1 R 2 is preferably higher than that of the byproduct trimethylsilyl halide.

[0080] For example, when the trimethylsilyl dialkylamine Me3SiNR 1 R 2 is Me3SiNMe2 (boiling point 84°C), the boiling point of the escaping trimethylsilyl halide is below 84°C, which is conducive to the forward progress of the reaction, and in this case, the halide is preferably MF6 and / or MCl6; when the trimethylsilyl dialkylamine Me3SiNR 1 R 2The boiling point of the trimethylsilyl halide that escapes for Me3SiNEt2(Et is ethyl, boiling point 125°C to 126°C) is below 125°C, which is advantageous for the reaction to proceed in the forward direction, and the halide is preferably MF6and / or MCI6, taking into account the boiling point of the halide and the tungsten content in the halide;

[0081] Thus, the halide MX6comprises MF6and / or MCI6.

[0082] Preferably, the R 1 is independently methyl and / or ethyl. 2 is independently methyl and / or ethyl.

[0083] Correspondingly, the trimethylsilyl dialkylamine Me3SiNR 1 R 2 is preferably any one or a combination of at least two of trimethylsilyldimethylamine, trimethylsilyldiethylamine or trimethylsilylmethylethylamine; the tetra(dialkylamino) halide M(NR 1 R 2 )4CI2is preferably any one or a combination of at least two of tetra(dimethylamino) halide, tetra(diethylamino) halide or tetra(methylethylamino) halide.

[0084] Preferably, the R 3 is any one or a combination of at least two of tert-butyl, tert-amyl, isopropyl, cyclohexyl or cyclopentyl.

[0085] Correspondingly, the trimethylsilyl monoalkylamine Me3SiNHR 3 is preferably any one or a combination of at least two of trimethylsilyl tert-butylamine, trimethylsilyl tert-amylamine, trimethylsilyl isopropylamine, trimethylsilyl cyclohexylamine or trimethylsilyl cyclopentylamine; the resulting diimino bis(dialkylamino) metal complex (R 3 N=)2M(NR 1 R 2 )2is t BuN=M(NR 1 R 2 )3, t AmN=)2M(NR 1 R 2 )2, i PrN=)2M(NR 1 R 2 )3, 1 CyN=)2M(NR 2 R 1 )2or 2 (CpN=)2M(NR

[0086] To ensure that the MX6 is fully converted to M(NR) 1 R 2 )4X2, reducing the formation of tungsten-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 MX6 is less than 4:1, a considerable proportion of M(NR) will be produced. 1 R 2 )3x3 or M(NR) 1 R 2 )2x4 or even MNR 1 R 2 X5 is generated, and then combined with Me3SiNHR 3 When the reaction occurs, bisimino halides or even more complex metal complexes are obtained. When Me3SiNR... 1 R 2 When the molar ratio of feed to MX6 is higher than 4.2:1, there will be varying degrees of M(NR) 1 R 2 )5X generated, then combined with Me3SiNHR 3 When a reaction occurs, the following reactions often take place:

[0087] M(NR 1 R 2 )5X+Me3SiNHR 3 →R 3 N = M(NR) 1 R 2 )4+Me3SiX+HNR 1 R 2 ,

[0088] even

[0089] M(NR 1 R 2 )6+Me3SiNHR 3 →R 3 N = M(NR) 1 R 2 )4+Me3SiNR 1 R 2 +HNR 1 R 2 ,

[0090] Or

[0091] M(NR 1 R 2)6+2Me3SiNHR 3 →(R 3 N=)2M(NR 1 R 2 )2+2Me3SiNR 1 R 2 +2HNR 1 R 2 .

[0092] To ensure the reaction favors the formation of (R 3 N=)2M(NR 1 R 2 )2, Me3SiNR 1 R 2 needs to be removed in time; however, the boiling point of Me3SiNHR 3 is not always higher than that of Me3SiNR 1 R 2 (for example, the boiling point of Me3SiNH i Pr is 98°C, and the boiling point of Me3SiNH t Bu is about 118°C to 119°C), making it difficult to remove Me3SiNR 1 R 2 by distillation, and raising the temperature will cause the reactant Me3SiNHR 3 to be removed together. Based on the intermediate M(NR 1 R 2 )4X2, ligand exchange is carried out, and the generated Me3SiX and HNR 1 R 2 have low boiling points and are easy to remove by distillation, making the reaction easily proceed in the forward direction.

[0093] Therefore, the molar ratio of the trimethylsilyl dialkylamine Me3SiNR 1 R 2 to the halide MX6 is preferably 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, and other values not listed in the range are also applicable.

[0094] In addition to being able to provide a dialkylamino ligand and being able to act as a dehalogenating agent, the trimethylsilyl dialkylamine can also act as a chemical water-removing agent in the reaction, and when there is trace water 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 replaced by two molecules of Me3SiNR 1 R 2 and hexamethyldisiloxane is obtained.

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

[0098] Preferably, the temperature of the reaction in step (1) is 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, and other values not listed in the value range are also applicable.

[0099] Me3SiNR 1 R 2 and MX6 can be carried out at a temperature range of 0°C to 150°C, when the reaction temperature in step (1) is lower than 0°C, there is a problem of Me3SiNR 1 R 2 precipitation in the inert solvent, and also reduces the volatilization of Me3SiX, affecting the smooth progress of the reaction; the higher the reaction temperature, the more conducive to the forward progress of the reaction, and the more conducive to the generation of tetrakis(dialkylamino) halide, but the temperature should not be higher than the boiling point of Me3SiNR 1 R 2 , otherwise it will lead to the escape of Me3SiNR 1 R 2 , causing the dehalogenation reaction to proceed smoothly, and there is a risk of destroying the intermediate product tetrakis(dialkylamino) halide, therefore, the temperature of the reaction in step (1) is preferably 20°C to 120°C.

[0100] Preferably, the reaction time of 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, and other values not listed in the value range are also applicable.

[0101] Preferably, the molar ratio of the halide MX6 to the trimethylsilyl monoalkylamine Me3SiNHR 3 is 1:2 to 1:2.2, for example, it can be 1:2, 1:2.1 or 1:2.2, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0102] to form diimino-bis(dialkylamino) metal complexes (R 3 N=)2M(NR 1 R 2 )2, the trimethylsilyl monoalkylamine needs to be added in strict stoichiometric ratio. If Me3SiNHR 3 is added too little, the amount of product (R 3 N=)2M(NR 1 R 2 )2will decrease and by-products such as R 3 N=M(NR 1 R 2 )3X will increase. If Me3SiNHR 3 is added too much, it can lead to the formation of triimino-substituted metal complexes (e.g. (R 3 N=)3M).

[0103] Further preferably, the trimethylsilyl monoalkylamine in step (2) is added dropwise to the solution of tetra(dialkylamino) halide M(NR 1 R 2 )4X2, so as to avoid local over-concentration of Me3SiNHR 3 in the reaction system and the formation of triimino-substituted metal complexes.

[0104] Preferably, the temperature of ligand exchange in step (2) is lower than the boiling point of Me3SiNH t Bu; further preferably, the temperature of ligand exchange in step (2) is higher than the boiling point of dialkylamine HNR 1 R 2 .

[0105] Preferably, the temperature of ligand exchange in step (2) is in the range of 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 values not listed in the range are also applicable.

[0106] The ligand exchange reaction between M(NR 1 R 2 )4X2 and Me3SiNHR 3 can be carried out in the temperature range of 0°C to 150°C. The minimum temperature of ligand exchange depends on the melting point of the inert solvent, but when the temperature is less than 0°C, the rate of ligand exchange will slow down and the reaction efficiency will decrease. For the ligand exchange reaction, a higher reaction temperature is beneficial to the formation of product, especially when the reaction temperature is higher than the boiling point of dialkylamine HNR 1 R 2 and Me3SiX, it is beneficial to the formation of HNR 1 R2 and Me3SiX, thus facilitating the forward progress of the ligand exchange reaction; but the temperature of the ligand exchange reaction should not exceed the boiling point of Me3SiNHR 3 , otherwise Me3SiNHR 3 will volatilize excessively, affecting the efficiency of the ligand exchange.

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

[0108] For example, when the trimethylsilyl monoalkylamine is Me3SiNH i Pr, the temperature of the ligand exchange should not exceed 98°C, and is preferably 0°C to 98°C; if the intermediate product is M(NMe2)4F2, the temperature of the ligand exchange is preferably 16°C to 98°C; if the intermediate product is M(NEtMe)4Cl2, the temperature of the ligand exchange is preferably 57°C to 98°C.

[0109] For example, when the trimethylsilyl monoalkylamine is Me3SiNH t Bu, the temperature of the ligand exchange should not exceed 119°C, and is preferably 0°C to 119°C; if the intermediate product is M(NMe2)4Br2, the temperature of the ligand exchange is preferably 79°C to 119°C; if the intermediate product is M(NEtMe)4F2, the temperature of the ligand exchange is preferably 36°C to 119°C; if the intermediate product is M(NEt2)4Cl2, the temperature of the ligand exchange is preferably 57°C to 119°C.

[0110] The temperature of the ligand exchange in step (2) of the present application can be constant during the ligand exchange, or can vary within a temperature range.

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

[0112] Preferably, the inert solvent in step (1) comprises a hydrocarbon solvent that does not participate in the reaction; preferably a hydrocarbon solvent with a boiling point lower than 150°C; further preferably a hydrocarbon solvent with a boiling point higher than the trimethylsilyl dialkylamine Me3SiNR 1 R 2Hydrocarbon solvents with a boiling point above 10°C.

[0113] The inert solvent in step (1) of this invention serves to disperse the reactants; although MX6 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 tungsten-containing complexes with other partial dehalogenation, and it is not easy to fully dehalogenate to form M(NR). 1 R 2 )4X2; 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 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 MX6 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 MX6 and reduce the formation of metal complexes from other dehalogenation processes, the mass ratio of MX6 to inert solvent in this invention shall not be less than 1:4. To ensure the product formation efficiency, the mass ratio of MX6 to inert solvent shall not exceed 1:40.

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

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

[0120] Preferably, the stirring speed of the stirring conditions is 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 values not listed in the value range are also applicable.

[0121] In a fourth aspect, the present application provides a device system for preparing diimino bis (dialkylamino) metal complex, which comprises a reaction unit, a pretreatment unit, a filtration unit, a purification unit and a nitrogen supply unit.

[0122] The reaction unit comprises a reaction device, 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 respectively independently connected with the reaction device through feed pipelines;

[0123] The nitrogen supply pipeline of the nitrogen supply unit is respectively connected with the feed pipeline of the trimethylsilyl dialkylamine supply device and the feed pipeline of the halide supply device;

[0124] The pretreatment unit comprises a condensation device and a first vacuum generating device connected in sequence; the condensation device comprises at least one condenser connected in series, and the bottom discharge port of the last condenser is connected with a light phase storage tank; the first vacuum generating device is used to control the vacuum degree of the condensation device;

[0125] The purification unit comprises a sublimator, a fractionation device, a second vacuum generating device, a first crystallization device, a second crystallization device and a third vacuum generating device; the light phase outlet of the sublimator is connected with the fractionation device; the second vacuum generating device is used to control the vacuum degree of the fractionation device; the sublimator is also connected with the first crystallization device and the second crystallization device; the third vacuum generating device is used to control the vacuum degrees of the first crystallization device and the second crystallization device;

[0126] The discharge port of the reaction device and the feed port of the evaporator are respectively independently connected with the filtration unit.

[0127] When the device system for preparation provided in the fourth aspect is used to prepare diimino bis (dialkylamino) metal complex:

[0128] For example, the reaction device provided in the present application is provided with a stirring device; the stirring device includes but is not limited to an anchor stirring device or a frame stirring device.

[0129] Preferably, the fractionating device comprises a rectifying column and a heavy phase storage tank.

[0130] The light phase outlet of the sublimer is connected with the feed inlet of the rectifying column.

[0131] The heavy phase outlet of the rectifying column is connected with the heavy phase storage tank.

[0132] The first crystallization device comprises a first crystallizer and a first product storage tank, and the second crystallization device comprises a second crystallizer and a second product storage tank; the first product storage tank is connected below the first crystallizer and the third vacuum generating device is connected above the first crystallizer; the second product storage tank is connected below the second crystallizer and the third vacuum generating device is connected above the second crystallizer.

[0133] The inert solvent is recovered in the heavy phase storage tank, the dialkylamino metal halide M(NR 1 R 2 )6 is obtained in the first product storage tank, and the diimino bis(dialkylamino) metal complex (R 3 N=)2M(NR 1 R 2 )2 is obtained in the second product storage tank.

[0134] Preferably, the filtering unit comprises at least two filters connected in parallel; the outlet of the reaction device and the inlet of the sublimer are respectively connected with two ends of the filters.

[0135] Preferably, the connecting pipeline of the filter and the reaction device and the connecting pipeline of the filter and the sublimer are respectively connected with the nitrogen supply pipeline of the nitrogen supply unit.

[0136] As a further preferred technical solution, the preparation method provided in the third aspect is carried out in the preparation device system provided in the fourth aspect.

[0137] Compared with the prior art, the present application has the following beneficial effects:

[0138] (1) The preparation method of the dialkylamino metal halide complex provided by the present application utilizes trimethylsilyl dialkylamine to prepare by dehalogenation of halide, the reaction is easy to control, the operation is simple, no solid waste such as lithium halide which is inconvenient to separate is produced, the product prepared has high purity, and industrial production can be easily realized;

[0139] (2) The preparation method of the diimino di(dialkylamino) metal complex provided by the application is a method for preparing an intermediate product dialkylamino metal halide by using trimethylsilyl dialkylamine to fully dehalogenate halides, and then performing ligand exchange with trimethylsilyl monoalkylamine to prepare the product; the method is a solid-liquid reaction of halides and dehalogenating agents, which is different from the solid-solid reaction of alkylamino lithium and halides, and is more easily uniformly dispersed; the dehalogenation reaction can be performed at a higher temperature within the range allowed by the boiling point of the dehalogenating agent, and the reaction rate is relatively fast; the method can avoid the introduction of metal impurities caused by the use of impure n-butyllithium in the technical route of dialkylamino lithium, and can also avoid the generation of lithium salts and other solid wastes that are not convenient for subsequent separation, thereby facilitating product purification, and the prepared product is easy to meet the purity requirements of tungsten-containing precursor materials in integrated circuit manufacturing;

[0140] The trimethylsilyl dialkylamine acts as a reactant, and serves as a dehalogenating agent for dehalogenating halides, a donor of dialkylamino ligands, and a chemical water removing agent; the reaction is performed with a slight excess of trimethylsilyl dialkylamine, which on the one hand ensures that the halides are fully dehalogenated, and on the other hand removes trace amounts of water remaining in the reaction device and materials, thereby facilitating the generation of the product; the trimethylsilyl monoalkylamine is used as a primary amine donor, and the reaction can be performed at a higher temperature within the range allowed by the boiling point, and the reaction rate is relatively fast;

[0141] (3) The reaction device for preparing high-purity dialkylamino metal halides and diimino di(dialkylamino) metal complexes provided by the application adopts the technical route of trimethylsilyl dialkylamine, and the reaction conditions are easy to control; the reaction unit and the purification unit are combined in the device, which can not only purify the product, but also recycle the by-products, unreacted trimethylsilyl dialkylamine, and solvents, and simultaneously collect low-boiling dialkylamine and trimethyl halosilane for regenerating trimethylsilyl dialkylamine. BRIEF DESCRIPTION OF DRAWINGS

[0142] The technical solutions of the application will be further described through specific embodiments.

[0143] Figure 1 The structural schematic diagram of the preparation device system of the diimino di(dialkylamino) metal complex provided by the application is shown in the figure.

[0144] In the figure, 11 is a reaction device, 12 is a trimethylsilyl dialkylamine supply device, 13 is a halide mixing tank, 14 is a solvent tank, and 15 is a trimethylsilyl monoalkylamine supply device.

[0145] 21 is a front condenser, 22 is a rear condenser, 23 is a light phase storage tank, 24 is a first cold trap, and 25 is a first vacuum generating device.

[0146] 31 is a first filter, and 32 is a second filter.

[0147] 41, sublimer; 42, waste tank; 43, fractionating column; 44, heavy phase storage tank; 45, second cold trap; 46, second vacuum generating device; 47, first crystallization device; 48, first product storage tank; 49, second crystallization device; 410, second product storage tank; 411, third cold trap; 412, third vacuum generating device. DETAILED DESCRIPTION

[0148] The technical solutions of the present application are further illustrated by the specific embodiments below.

[0149] The preparation method of the dialkylamino metal halide and the preparation method of the diimino bis (dialkylamino) metal complex in the specific embodiments of the present application can be carried out in the diimino bis (dialkylamino) metal complex preparation device system as shown in the figure. Figure 1 That is, the dialkylamino metal halide device system and the diimino bis (dialkylamino) metal complex device system have the same parts, and when using the diimino bis (dialkylamino) metal complex preparation device system to prepare the dialkylamino metal halide, only the corresponding device units are used.

[0150] The diimino bis (dialkylamino) metal complex device system as shown in the figure includes a reaction unit, a pretreatment unit, a filtration unit, a purification unit, and a nitrogen supply unit. Figure 1

[0151] 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 respectively independently connected to the reaction device 11 through feed pipelines;

[0152] 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 discharge port of the halide mixing tank 13 is connected to the reaction device 11 through a feed pipeline.

[0153] The nitrogen supply pipeline of the nitrogen supply unit is respectively connected to the feed pipeline of the trimethylsilyl dialkylamine supply device 12 and the feed pipeline of the halide supply device;

[0154] ​The pre-treatment unit comprises a condensing device and a first vacuum generating device 25 connected in sequence; the condensing device comprises a front condenser 21 and a rear condenser 22 connected in series, and the bottom discharge port of the rear condenser 22 is connected with a light phase storage tank 23; the first vacuum generating device 25 is used for controlling the vacuum degree of the condensing device; a first cold trap 24 is arranged between the first vacuum generating device 25 and the condenser for protecting the first vacuum generating device 25;

[0155] The purification unit comprises a sublimer 41, a waste tank 42, a fractionating device 43, a second vacuum generating device 46, a first crystallization device 47, a second crystallization device 49 and a third vacuum generating device 412; the light phase outlet of the sublimer 41 is connected with the fractionating device 43, and the bottom discharge port of the sublimer 41 is connected with the waste tank 42; the second vacuum generating device 46 is used for controlling the vacuum degree of the fractionating device 43; a second cold trap 45 is arranged in the connecting pipeline between the second vacuum generating device 46 and the fractionating device 43 for protecting the second vacuum generating device 46; the bottom discharge port of the fractionating device 43 is connected with a heavy phase storage tank 44; the sublimer 41 is connected with the first crystallization device 47 and the second crystallization device 49 respectively; the third vacuum generating device 412 is used for controlling the vacuum degrees of the first crystallization device 47 and the second crystallization device 49; the first crystallization device 47 comprises a first crystallizer and a first product storage tank 48, and the second crystallization device 49 comprises a second crystallizer and a second product storage tank 410; the first product storage tank 48 is connected below the first crystallizer, and the third vacuum generating device 412 is connected above the first crystallizer; the second product storage tank 410 is connected below the second crystallizer, and the third vacuum generating device 412 is connected above the second crystallizer; a third cold trap 411 is arranged in the connecting pipeline between the third vacuum generating device 412 and the first crystallizer and the second crystallizer for protecting the third vacuum generating device 412;

[0156] The discharge port of the reaction device 11 and the feed port of the sublimer 41 are respectively independently connected with a filtering unit; the filtering unit comprises two first filters 31 and second filters 32 connected in parallel; the discharge port of the reaction device 11 and the feed port of the sublimer 41 are respectively connected with two ends of the filters;

[0157] The heavy phase storage tank 44 recovers inert solvents, the first product storage tank 48 obtains dialkylamino metal halides, and the second product storage tank 410 obtains diimino bis(dialkylamino) metal complexes (R 3 N=)2W(NR 1 R 2 )2.

[0158] The connecting pipelines of the filters and the reaction device 11 and the connecting pipelines of the filters and the sublimer 41 are respectively connected with nitrogen supply pipelines of a nitrogen supply unit.

[0159] The preparation device system for preparing the diimino bis (dialkylamino) metal complex comprises the following steps:

[0160] (a) nitrogen replacement is performed on each unit and connecting pipeline involved in the preparation device system, and inert solvent, halide, trimethylsilyl dialkylamine and trimethylsilyl monoalkylamine are prepared according to the feeding amount;

[0161] (b) part of the inert solvent in the solvent tank and the halide are dispersed in the halide mixing tank, and then transferred to the reaction device, and then the remaining solvent is used to flush the halide mixing tank and transferred to the reaction device; trimethylsilyl dialkylamine is added to the reaction device, and the temperature in the reaction device is controlled to make the reaction proceed; after the reaction is completed, the generated trimethyl halosilane is removed by distillation, the temperature in the reaction device is adjusted to below the boiling point of trimethylsilyl monoalkylamine, and the ligand exchange reaction is performed;

[0162] (c) after the low-boiling-point components in the reaction device are removed by distillation, the product solution is filtered by the filtering unit, and then enters the sublimator;

[0163] (d) the temperature and pressure of the sublimator are controlled to perform the reduced pressure distillation, the inert solvent is taken out from the light phase outlet at the top of the sublimator and enters the fractionating device, and the recovered inert solvent passes through the fractionating device; the dialkylamino metal halide in the solid in the sublimator is treated by the first crystallization device and collected in the first product tank, and the diimino bis (dialkylamino) metal complex in the remaining solid is treated by the second crystallization device and collected in the second product tank.

[0164] Example 1-1

[0165] The embodiment provides a preparation method of hexakis (dimethylamino) tungsten, and the preparation method comprises the following steps:

[0166] Under the condition of a nitrogen atmosphere, 31.7 g (0.08 mol) of WCl6 reacts with 84.4 g (0.72 mol) of Me3SiNMe2 in 317 g (463 mL) of inert solvent n-heptane in a 1L reaction device, after the by-product Me3SiCl is no longer evaporated, the unreacted Me3SiNMe2 is distilled by heating, and a hexakis (dimethylamino) tungsten W(NMe2)6 solution is obtained.

[0167] The obtained hexakis (dimethylamino) tungsten W(NMe2)6 solution is subjected to reduced pressure distillation and sublimation in a sublimator, and hexakis (dimethylamino) tungsten is obtained in the first crystallization device.

[0168] The reaction is performed under stirring, the stirring speed of the stirring condition is 100 rpm, the temperature of the reaction is 60 DEG C, and the time is 6 h.

[0169] In this embodiment, the molar ratio of Me3SiNMe2 to WCl6 is 9:1; the mass ratio of WCl6 to n-heptane is 1:10.

[0170] Example 1-2

[0171] This embodiment provides a preparation method of hexakis(dimethylamino)tungsten, which comprises the following steps:

[0172] Under the condition of nitrogen atmosphere, 63.4 g (0.16 mol) of WCl6 is reacted with 112.6 g (0.96 mol) of Me3SiNMe2 in 254 g (371 mL) of inert solvent n-heptane in a 1L reaction device, after the by-product Me3SiCl is no longer distilled out, the unreacted Me3SiNMe2 is distilled by heating, and a hexakis(dimethylamino)tungsten W(NMe2)6 solution is obtained.

[0173] The obtained hexakis(dimethylamino)tungsten W(NMe2)6 solution is subjected to reduced pressure distillation and sublimation in a sublimator, and hexakis(dimethylamino)tungsten is obtained in a first crystallization device.

[0174] The reaction is carried out under stirring condition, the stirring speed of the stirring condition is 100 rpm; the temperature of the reaction is 60°C, and the time is 6h.

[0175] In this embodiment, the molar ratio of Me3SiNMe2 to WCl6 is 9:1; the mass ratio of WCl6 to n-heptane is 1:10.

[0176] Example 1-3

[0177] This embodiment provides a preparation method of hexakis(dimethylamino)tungsten, which comprises the following steps:

[0178] Under the condition of nitrogen atmosphere, 63.4 g (0.16 mol) of WCl6 is reacted with 112.6 g (0.96 mol) of Me3SiNMe2 in 254 g (371 mL) of inert solvent n-heptane in a 1L reaction device, after the by-product Me3SiCl is no longer distilled out, the unreacted Me3SiNMe2 is distilled by heating, and a hexakis(dimethylamino)tungsten W(NMe2)6 solution is obtained.

[0179] The obtained hexakis(dimethylamino)tungsten W(NMe2)6 solution is subjected to reduced pressure distillation and sublimation in a sublimator, and hexakis(dimethylamino)tungsten is obtained in a first crystallization device.

[0180] The reaction is carried out under stirring condition, the stirring speed of the stirring condition is 100 rpm; the temperature of the reaction is 60°C, and the time is 6h.

[0181] In this embodiment, the molar ratio of Me3SiNMe2 to WCl6 is 14:1; the mass ratio of WCl6 to n-heptane is 1:40.

[0182] Example 1-4

[0183] This embodiment provides a preparation method of hexakis(dimethylamino)tungsten, which is the same as Example 1-1 except that Me3SiNMe2 is replaced by Me3SiNEtMe in equal molar amount and n-heptane is replaced by n-octane in equal mass.

[0184] Example 1-5

[0185] This embodiment provides a preparation method of hexakis(diethylamino)tungsten, which is the same as Example 1-1 except that Me3SiNMe2 is replaced by Me3SiNEt2 in equal molar amount and n-heptane is replaced by n-nonane in equal mass.

[0186] Example 1-6

[0187] This embodiment provides a preparation method of hexakis(dimethylamino)tungsten, which comprises the following steps:

[0188] Under the condition of nitrogen atmosphere, 31.7g (106.4mmol) WF6 reacts with 112.3g (0.958mol) Me3SiNMe2 in 317g (481mL) inert solvent n-hexane in a 1L reaction device, after the by-product Me3SiF is no longer evaporated, the unreacted Me3SiNMe2 is distilled by heating, to obtain a hexakis(dimethylamino)tungsten W(NMe2)6 solution;

[0189] The obtained hexakis(dimethylamino)tungsten W(NMe2)6 solution is subjected to reduced pressure distillation and sublimation in a sublimator, to obtain hexakis(dimethylamino)tungsten in a first crystallization device.

[0190] The reaction is carried out under stirring condition, the stirring speed of the stirring condition is 100rpm; the temperature of the reaction is 60℃, and the time is 6h.

[0191] In this embodiment, the molar ratio of Me3SiNMe2 to WF6 is 9:1; the mass ratio of WF6 to n-hexane is 1:10.

[0192] Example 1-7

[0193] This embodiment provides a preparation method of hexakis(dimethylamino)tungsten, which comprises the following steps:

[0194] In a 1L reaction device, 31.7g (47.8mmol) of WBr6 was reacted with 50.4g (0.430mol) of Me3SiNMe2 in 317g (364mL) of inert solvent toluene under the condition of nitrogen atmosphere, and unreacted Me3SiNMe2 and byproduct Me3SiBr generated were distilled off by heating, to obtain a solution of hexakis(dimethylamino)tungsten W(NMe2)6.

[0195] The obtained solution of hexakis(dimethylamino)tungsten W(NMe2)6 was subjected to sublimation under reduced pressure in a sublimator, and hexakis(dimethylamino)tungsten was obtained in a first fractionating device.

[0196] The reaction was carried out under stirring at a stirring speed of 100rpm, and the reaction temperature was 80℃ and the reaction time was 6h.

[0197] In this example, the molar ratio of Me3SiNMe2 to WBr6 was 9:1, and the mass ratio of WBr6 to toluene was 1:10.

[0198] Example 1-8

[0199] This example provides a preparation method of hexakis(dimethylamino)tungsten, which is the same as example 1-1 except that the amount of Me3SiNMe2 is changed, and the molar ratio of Me3SiNMe2 to WCl6 is 5:1.

[0200] In this example, WCl6 was not completely dechlorinated, and no product was generated.

[0201] Example 1-9

[0202] This example provides a preparation method of hexakis(dimethylamino)tungsten, which is the same as example 1-3 except that the amount of Me3SiNMe2 is changed, and the molar ratio of Me3SiNMe2 to WCl6 is 15:1.

[0203] In this example, the amount of Me3SiNMe2 was too large, which affected the preparation efficiency of the product.

[0204] Example 1-10

[0205] This example provides a preparation method of hexakis(dimethylamino)tungsten, which is the same as example 1-2 except that the amount of n-heptane is changed, and the mass ratio of WCl6 to n-heptane is 1:3.

[0206] Example 1-11

[0207] This embodiment provides a method for preparing hexa(dimethylamino)tungsten. Except for changing the amount of n-heptane to make the mass ratio of WCl6 to n-heptane 1:42, the rest is the same as in Examples 1-3.

[0208] In this embodiment, the amount of n-heptane added was too large, which affected the product preparation efficiency.

[0209] The mass of the hexa(dialkylamino)tungsten prepared in the above examples, the yield calculated based on the tungsten halide feed, and the HPLC purity were determined, and the results are shown in Table 1.

[0210] Table 1

[0211] Product mass (g) Yield (%) HPLC purity (wt%) Example 1-1 33.0 92 99.99 Example 1-2 61.0 85 99.3 Example 1-3 10.1 90 99.99 Example 1-4 40.3 92 99.99 Example 1-5 43.9 89 99.99 Example 1-6 43.4 91 99.99 Example 1-7 16.7 78 99.92 Example 1-8 —— —— —— Example 1-9 10.2 91 99.99 Example 1-10 61.7 86 98.7 Example 1-11 10.1 90 99.99

[0212] The “——” in Table 1 indicates that no product was generated in Examples 1-8, therefore no relevant measurement results were obtained.

[0213] Example 2-1

[0214] This embodiment provides a method for preparing a diiminotris(dimethylamino)tungsten complex, the method comprising the following steps:

[0215] (1) Under nitrogen atmosphere, in a 1L reaction apparatus, 31.7g (0.08mol) WCl6 and 38.5g (0.328mol) Me3SiNMe2 reacted in 317g (463mL) of inert solvent n-heptane. After the byproduct Me3SiCl no longer evaporated, the unreacted Me3SiNMe2 was heated and distilled to obtain a tetra(dimethylamino)tungsten chloride W(NMe2)4Cl2 solution.

[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 24.4 g (0.168 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 di(tert-butylimino)di(dimethylamino)tungsten complex was obtained in a second crystallization apparatus. t BuN=)2W(NMe2)2.

[0220] In this embodiment, the molar ratio of Me3SiNMe2 to WCl6 is 4.1:1; the mass ratio of WCl6 to n-heptane is 1:10; the molar ratio of WCl6 to Me3SiNH t The molar ratio of Bu to WCl6 is 1:2.1.

[0221] Example 2-2

[0222] This embodiment provides a preparation method of a diimido di(dimethylamino) tungsten complex, which comprises the following steps:

[0223] (1) Under the condition of nitrogen atmosphere, 63.4 g (0.16 mol) of WCl6 is reacted with 75.1 g (0.64 mol) of Me3SiNMe2 in 254 g (371 mL) of inert solvent n-heptane in a 1 L reaction device, and after the by-product Me3SiCl is no longer distilled out, the unreacted Me3SiNMe2 is distilled out by heating, to obtain a tungsten tetrakis(dimethylamino) chloride W(NMe2)4Cl2 solution;

[0224] The reaction is carried out under stirring conditions, and the stirring speed of the stirring conditions is 100 rpm; the temperature of the reaction is 60°C, and the time is 6 h.

[0225] (2) Under the condition of nitrogen atmosphere, the temperature is maintained at 60°C to carry out the reaction of 46.5 g (0.32 mol) of trimethylsilyl tert-butylamine Me3SiNH t Bu is added dropwise, and stirring is continuously carried out during the dropwise addition; after 2 h of dropwise addition, ligand exchange is carried out to obtain a product solution;

[0226] The ligand exchange is carried out under stirring conditions, and the stirring speed of the stirring conditions is 100 rpm; the temperature of the ligand exchange is 60°C for 2 h, and then 80°C for 2 h;

[0227] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and di(tert-butylimino) di(dimethylamino) tungsten complex ( t BuN=)2W(NMe2)2) is obtained in a second crystallization device.

[0228] In this embodiment, the molar ratio of Me3SiNMe2 to WCl6 is 4:1; the mass ratio of WCl6 to n-heptane is 1:4; the molar ratio of WCl6 to Me3SiNH t The molar ratio of Bu to WCl6 is 1:2.

[0229] Example 2-3

[0230] This embodiment provides a preparation method of a diimido di(dimethylamino) tungsten complex, which comprises the following steps:

[0231] (1) Under the condition of nitrogen atmosphere, 9.91 g (0.025 mol) of WCl6 was reacted with 12.3 g (0.105 mol) of Me3SiNMe2 in 396 g (580 mL) of inert solvent n-heptane in a 1 L reaction device, after the by-product Me3SiCl was no longer distilled out, the unreacted Me3SiNMe2 was distilled out by heating, to obtain a solution of W(NMe2)4Cl2;

[0232] The reaction was carried out under stirring condition, the stirring speed of the stirring condition was 100 rpm; the temperature of the reaction was 60°C, and the time was 6 h.

[0233] (2) Under the condition of nitrogen atmosphere, 8.0 g (0.055 mol) of Me3SiNH t Bu was added dropwise, stirring was continued during the dropwise addition, and the ligand exchange was carried out after 2 h of dropwise addition to obtain a product solution;

[0234] The ligand exchange was carried out under stirring condition, the stirring speed of the stirring condition was 100 rpm; the temperature of the ligand exchange was 60°C for 2 h, and then 80°C for 2 h;

[0235] The obtained product solution was subjected to vacuum distillation and sublimation in a sublimator, and (tert-buty limino)bis(dimethylamino) tungsten complex (BuN=)2W(NMe2)2) was obtained in a second crystallization device. t BuN=)2W(NMe2)2.

[0236] In this embodiment, the molar ratio of Me3SiNMe2 to WCl6 was 4.2:1; the mass ratio of WCl6 to n-heptane was 1:40, and the molar ratio of WCl6 to Me3SiNH t Bu was 1:2.2.

[0237] Example 2-4

[0238] The embodiment provides a preparation method of a diimino bis(dimethylamino) tungsten complex, and the preparation method comprises the following steps:

[0239] (1) Under the condition of nitrogen atmosphere, 31.7 g (0.08 mol) of WCl6 was reacted with 38.5 g (0.328 mol) of Me3SiNMe2 in 317 g (463 mL) of inert solvent n-heptane in a 1 L reaction device, after the by-product Me3SiCl was no longer distilled out, the unreacted Me3SiNMe2 was distilled out by heating, to obtain a solution of W(NMe2)4Cl2;

[0240] The reaction is carried out under stirring conditions, and the stirring speed of the stirring conditions is 100 rpm; the temperature of the reaction is 60°C, and the time is 6 h;

[0241] (2) Under the condition of nitrogen atmosphere, 24.4 g (0.168 mol) of trimethylsilyl isopropylamine Me3SiNH i Pr is added dropwise, stirring is continuously carried out during the dropwise addition, ligand exchange is carried out after 2 h of dropwise addition, and a product solution is obtained;

[0242] The ligand exchange is carried out under stirring conditions, and the stirring speed of the stirring conditions is 100 rpm; the temperature of the ligand exchange is 60°C for 2 h and then 80°C for 2 h;

[0243] The obtained product solution is subjected to vacuum distillation and sublimation in a sublimator, and bis(isopropylimino)bis(dimethylamino) tungsten complex (PrN=)2W(NMe2)2 is obtained in a second crystallization device. i The obtained product solution is subjected to vacuum distillation and sublimation in a sublimator, and bis(isopropylimino)bis(dimethylamino) tungsten complex (PrN=)2W(NMe2)2 is obtained in a second crystallization device.

[0244] In this embodiment, the molar ratio of Me3SiNMe2 to WCl6 is 4.1:1; the mass ratio of WCl6 to n-heptane is 1:10; and the molar ratio of WCl6 to Me3SiNH i The molar ratio of Pr is 1:2.1.

[0245] Example 2-5

[0246] The embodiment provides a preparation method of a diimino tris(methylethylamino) tungsten complex, and the preparation method comprises the following steps:

[0247] (1) Under the condition of nitrogen atmosphere, 31.7 g (0.08 mol) of WCl6 is reacted with 43.1 g (0.328 mol) of Me3SiNEtMe in 317 g (451 mL) of inert solvent n-octane in a 1L reaction device, after the by-product Me3SiCl is no longer distilled out, the unreacted Me3SiNEtMe is distilled out by heating, and a tungsten tetrakis(methylethylamino) chloride W(NEtMe)4Cl2 solution is obtained;

[0248] The reaction is carried out under stirring conditions, and the stirring speed of the stirring conditions is 100 rpm; the temperature of the reaction is 60°C, and the time is 6 h;

[0249] (2) Under the condition of nitrogen atmosphere, 26.8 g (0.168 mol) of trimethylsilyl tert-pentylamine Me3SiNH t Am is added dropwise, stirring is continuously carried out during the dropwise addition, ligand exchange is carried out after 2 h of dropwise addition, and a product solution is obtained;

[0250] The ligand exchange is carried out under stirring at a stirring speed of 100 rpm, and the ligand exchange is carried out at a temperature of 60 °C for 2 h and then at a temperature of 80 °C for 2 h.

[0251] The obtained product solution is subjected to vacuum distillation and sublimation in a sublimator, and a bis(cyclopentyl imino) bis(dimethyl ethyl amino) tungsten complex (CpN=)2W(NEtMe)2 is obtained in a second crystallization device. t AmN=)2W(NEtMe)2.

[0252] In this embodiment, the molar ratio of Me3SiNEtMe to WCl6 is 4.1:1, the mass ratio of WCl6 to n-octane is 1:10, and the molar ratio of WCl6 to Me3SiNH t The molar ratio of Am is 1:2.1.

[0253] Example 2-6

[0254] The embodiment provides a preparation method of an imino tris(methyl ethyl amino) tungsten complex, and the preparation method comprises the following steps:

[0255] (1) Under a nitrogen atmosphere, 31.7 g (0.08 mol) of WCl6 is reacted with 43.1 g (0.328 mol) of Me3SiNEtMe in 317 g (451 mL) of an inert solvent n-octane in a 1L reaction device, and after the by-product Me3SiCl is no longer distilled out, the unreacted Me3SiNEtMe is distilled out by heating, to obtain a tungsten chloride tetra(methyl ethyl amino) W(NEtMe)4Cl2 solution;

[0256] The reaction is carried out under stirring at a stirring speed of 100 rpm, and the reaction is carried out at a temperature of 60 °C for 6 h.

[0257] (2) Under a nitrogen atmosphere, 26.4 g (0.168 mol) of trimethylsilyl cyclopentyl amine Me3SiNHCp is added dropwise while stirring at a temperature of 60 °C, and after 2 h of dropwise addition, ligand exchange is carried out to obtain a product solution;

[0258] The ligand exchange is carried out under stirring at a stirring speed of 100 rpm, and the ligand exchange is carried out at a temperature of 60 °C for 2 h and then at a temperature of 80 °C for 2 h.

[0259] The obtained product solution is subjected to vacuum distillation and sublimation in a sublimator, and a bis(cyclopentyl imino) bis(dimethyl ethyl amino) tungsten complex (CpN=)2W(NEtMe)2 is obtained in a second crystallization device.

[0260] In this embodiment, the molar ratio of Me3SiNEtMe to WCl6 is 4.1:1; the mass ratio of WCl6 to n-octane is 1:10; and the molar ratio of WCl6 to Me3SiNHCp is 1:2.1.

[0261] Example 2-7

[0262] This embodiment provides a preparation method of a diimino tris(dimethylamino) tungsten complex, which comprises the following steps:

[0263] (1) Under the condition of nitrogen atmosphere, 31.7 g (0.08 mol) of WCl6 is reacted with 47.7 g (0.328 mol) of Me3SiNEt2 in 317 g (440 mL) of inert solvent n-nonyl in a 1L reaction device, and after the by-product Me3SiCl is no longer evaporated, the unreacted Me3SiNEt2 is distilled by heating to obtain a tungsten tetrakis (diethylamino) chloride solution;

[0264] The reaction is carried out under stirring condition, and the stirring speed of the stirring condition is 100 rpm; the temperature of the reaction is 60°C, and the time is 6h;

[0265] (2) Under the condition of nitrogen atmosphere, the temperature is maintained at 60°C to perform dropwise addition of 28.8 g (0.168 mol) of trimethylsilyl cyclohexylamine Me3SiNHCy, and stirring is continuously performed during the dropwise addition, and after 2h of dropwise addition, ligand exchange is performed to obtain a product solution;

[0266] The ligand exchange is carried out under stirring condition, and the stirring speed of the stirring condition is 100 rpm; the temperature of the ligand exchange is 60°C for 2h, and then 80°C for 2h;

[0267] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and diimino bis (diethylamino) tungsten complex (CyN=) 2W (NEt2) 2 is obtained in a second crystallization device.

[0268] In this embodiment, the molar ratio of Me3SiNEt2 to WCl6 is 4.1:1; the mass ratio of WCl6 to n-nonyl is 1:10; and the molar ratio of WCl6 to Me3SiNHCy is 1:2.1.

[0269] Example 2-8

[0270] This embodiment provides a preparation method of a diimino tris(dimethylamino) tungsten complex, which comprises the following steps:

[0271] (1) under the condition of nitrogen atmosphere, 31.7 g (106.4 mmol) WF6 was reacted with 51.1 g (0.436 mol) Me3SiNMe2 in 317 g (481 mL) inert solvent n-hexane in a 1 L reaction device, after the by-product Me3SiF was no longer evaporated, the unreacted Me3SiNMe2 was distilled by heating to obtain a solution of tetra(dimethylamino) tungsten fluoride;

[0272] The reaction was carried out under stirring condition, the stirring speed of the stirring condition was 100 rpm; the temperature of the reaction was 30℃, and the time was 6 h;

[0273] (2) under the condition of nitrogen atmosphere, 32.5 g (0.223 mol) trimethylsilyl tert-butylamine Me3SiNH t The dropwise addition of Bu was carried out under stirring, and the ligand exchange was carried out after 2 h of dropwise addition to obtain a product solution;

[0274] The ligand exchange was carried out under stirring condition, the stirring speed of the stirring condition was 100 rpm; the temperature of the ligand exchange was 30℃ for 2 h, and then 60℃ for 2 h;

[0275] The obtained product solution was subjected to vacuum distillation and sublimation in a sublimator, and a bis(tert-butylimino) bis(dimethylamino) tungsten complex was obtained in a second crystallization device.

[0276] In this embodiment, the molar ratio of Me3SiNMe2 to WF6 was 4.1:1; the mass ratio of WF6 to n-hexane was 1:10; and the molar ratio of WF6 to Me3SiNH t The molar ratio of Bu was 1:2.1.

[0277] Example 2-9

[0278] The embodiment provides a preparation method of a diimino bis(dimethylamino) tungsten complex, and the preparation method comprises the following steps:

[0279] (1) under the condition of nitrogen atmosphere, 31.7 g (47.8 mmol) WBr6 was reacted with 23.0 g (0.196 mol) Me3SiNMe2 in 317 g (364 mL) inert solvent toluene in a 1 L reaction device, and the unreacted Me3SiNMe2 and the by-product Me3SiBr generated were distilled by heating to obtain a solution of tetra(dimethylamino) tungsten bromide;

[0280] The reaction was carried out under stirring condition, the stirring speed of the stirring condition was 100 rpm; the temperature of the reaction was 80℃, and the time was 6 h;

[0281] (2) nitrogen atmosphere, maintaining the temperature of 80℃ to carry out 14.6g (100.4mmol) trimethylsilyl tertiary butyl amine Me3SiNH t Bu was added dropwise, and stirring was continuously carried out during the dropwise addition. Ligand exchange was carried out after 2h of dropwise addition, and a product solution was obtained.

[0282] The ligand exchange was carried out under stirring conditions, and the stirring speed of the stirring conditions was 100rpm. The temperature of the ligand exchange was 80℃ for 2h, and then 100℃ for 2h.

[0283] The obtained product solution was subjected to reduced pressure distillation and sublimation in a sublimator, and bis(tert-butylimido)bis(dimethylamino)tungsten complex was obtained in a second crystallization device.

[0284] In this embodiment, the molar ratio of Me3SiNMe2 to WBr6 was 4.1:1; the mass ratio of WBr6 to toluene was 1:10; the molar ratio of WBr6 to Me3SiNH t The molar ratio of WBr6 to Me3SiNH

[0285] Example 2-10

[0286] This embodiment provides a preparation method of bis(imido)bis(dimethylamino)tungsten complex, wherein the molar ratio of Me3SiNMe2 to WBr6 is changed to 4.1:1; the mass ratio of WBr6 to toluene is 1:10; the molar ratio of WBr6 to Me3SiNH t The molar ratio of WBr6 to Me3SiNH t The molar ratio of WBr6 to Me3SiNH

[0287] Example 2-11

[0288] This embodiment provides a preparation method of bis(imido)bis(dimethylamino)tungsten complex, wherein the molar ratio of Me3SiNMe2 to WBr6 is changed to 4.1:1; the mass ratio of WBr6 to toluene is 1:10; the molar ratio of WBr6 to Me3SiNH t The molar ratio of WBr6 to Me3SiNH t The molar ratio of WBr6 to Me3SiNH

[0289] The mass, yield calculated according to the feeding of tungsten halide, and HPLC purity of the tris(dialkylamino)tungsten complex prepared in the above embodiments were determined, and the results are shown in Table 2.

[0290] Table 2

[0291] Product mass (g) Yield (%) Purity (wt%) Example 2-1 30.2 91 99.99 Example 2-2 55.7 84 99.3 Example 2-3 9.3 90 99.99 Example 2-4 27.5 89 99.99 Example 2-5 33.1 88 99.97 Example 2-6 33.6 90 99.95 Example 2-7 35.5 85 99.93 Example 2-8 41.0 93 99.99 Example 2-9 15.8 80 99.6 Example 2-10 22.5 68 99.99 Example 2-11 21.5 65 99.99

[0292] Example 3-1

[0293] This embodiment provides a preparation method of hexakis(dimethylamino)molybdenum, which comprises the following steps:

[0294] Under the condition of nitrogen atmosphere, 30.9 g (0.10 mol) of MoCl6 was reacted with 105.5 g (0.90 mol) of Me3SiNMe2 in 309 g (452 mL) of inert solvent n-heptane in a 1 L reaction device, after the by-product Me3SiCl was no longer evaporated, the unreacted Me3SiNMe2 was distilled by temperature rising, to obtain a hexakis(dimethylamino)molybdenum Mo(NMe2)6 solution;

[0295] The obtained hexakis(dimethylamino)molybdenum Mo(NMe2)6 solution was subjected to vacuum distillation and sublimation in a sublimator, and hexakis(dimethylamino)molybdenum was obtained in a first crystallization device.

[0296] The reaction was carried out under stirring condition, the stirring speed of the stirring condition was 100 rpm; the temperature of the reaction was 60°C, and the time was 6 h.

[0297] In this embodiment, the molar ratio of Me3SiNMe2 to MoCl6 was 9:1; the mass ratio of MoCl6 to n-heptane was 1:10.

[0298] Example 3-2

[0299] The embodiment provides a preparation method of hexakis(methylethylamino)molybdenum, which is the same as that in Example 3-1, except that Me3SiNMe2 is replaced by Me3SiNEtMe in equal molar amount, and n-heptane is replaced by n-octane in equal mass.

[0300] Example 3-3

[0301] The embodiment provides a preparation method of hexakis(diethylamino)molybdenum, which is the same as that in Example 3-1, except that Me3SiNMe2 is replaced by Me3SiNEt2 in equal molar amount, and n-heptane is replaced by n-nonane in equal mass.

[0302] Example 3-4

[0303] The embodiment provides a preparation method of hexakis(dimethylamino)molybdenum, which comprises the following steps:

[0304] Under the condition of nitrogen atmosphere, 30.9 g (0.10 mol) of MoCl6 was reacted with 105.5 g (0.90 mol) of Me3SiNMe2 in 309 g (452 mL) of inert solvent n-heptane in a 1 L reaction device, after the by-product Me3SiCl was no longer evaporated, the unreacted Me3SiNMe2 was distilled by temperature rising, to obtain a hexakis(dimethylamino)molybdenum Mo(NMe2)6 solution;

[0305] The obtained hexakis(dimethylamino)molybdenum Mo(NMe2)6 solution is subjected to reduced pressure distillation and sublimation in a sublimator, and hexakis(dimethylamino)molybdenum is obtained in a first crystallization device.

[0306] The reaction is carried out under stirring at a stirring speed of 100 rpm, and the reaction temperature is 60°C and the reaction time is 6h.

[0307] In this embodiment, the molar ratio of Me3SiNMe2 to MoF6 is 9:1, and the mass ratio of MoF6 to n-hexane is 1:10.

[0308] Example 3-5

[0309] The embodiment provides a preparation method of hexakis(dimethylamino)molybdenum, and the preparation method comprises the following steps:

[0310] Under a nitrogen atmosphere, 30.9g (53.7mmol) of MoBr6 is reacted with 56.7g (0.483mol) of Me3SiNMe2 in 309g (355mL) of inert solvent toluene in a 1L reaction device, and unreacted Me3SiNMe2 and generated byproduct Me3SiBr are subjected to warming distillation to obtain a hexakis(dimethylamino)molybdenum Mo(NMe2)6 solution.

[0311] The obtained hexakis(dimethylamino)molybdenum Mo(NMe2)6 solution is subjected to reduced pressure distillation and sublimation in a sublimator, and hexakis(dimethylamino)molybdenum is obtained in a first crystallization device.

[0312] The reaction is carried out under stirring at a stirring speed of 100 rpm, and the reaction temperature is 80°C and the reaction time is 6h.

[0313] In this embodiment, the molar ratio of Me3SiNMe2 to MoBr6 is 9:1, and the mass ratio of MoBr6 to toluene is 1:10.

[0314] The mass, yield calculated according to the molar ratio of the halogenated molybdenum and HPLC purity of the hexakis(dialkylamino)molybdenum prepared in the above embodiment are determined, and the obtained results are shown in Table 3.

[0315] Table 3

[0316] Product mass (g) Yield (%) HPLC purity (wt%) Example 3-1 32.4 90 99.99 Example 3-2 39.1 88 99.99 Example 3-3 44.9 85 99.95 Example 3-4 33.2 92 99.99 Example 3-5 26.3 73 99.8

[0317] Example 4-1

[0318] The embodiment provides a preparation method of a diimidotri(dimethylamino)molybdenum complex, and the preparation method comprises the following steps:

[0319] (1) under the condition of nitrogen atmosphere, 30.9 g (0.10 mol) MoCl6 reacts with 48.1 g (0.41 mol) Me3SiNMe2 in 309 g (452 mL) inert solvent n-heptane in a 1 L reaction device, after the by-product Me3SiCl no longer evaporates, the unreacted Me3SiNMe2 is distilled by heating to obtain a solution of Mo(NMe2)4Cl2;

[0320] The reaction is carried out under stirring conditions, and the stirring speed of the stirring conditions is 100 rpm; the temperature of the reaction is 60°C, and the time is 6 h;

[0321] (2) under the condition of nitrogen atmosphere, 30.5 g (0.21 mol) trimethylsilyl tert-butylamine Me3SiNH t Bu is added dropwise, stirring is continued during the dropwise addition, and the ligand exchange is carried out after 2 h of dropwise addition to obtain a product solution;

[0322] The ligand exchange is carried out under stirring conditions, and the stirring speed of the stirring conditions is 100 rpm; the temperature of the ligand exchange is 60°C for 2 h, and then 80°C for 2 h;

[0323] The obtained product solution is subjected to vacuum distillation and sublimation in a sublimator, and the di(tert-butylimino)di(dimethylamino) molybdenum complex (BuN=)2Mo(NMe2)2 is obtained in a second crystallization device. t BuN=)2Mo(NMe2)2.

[0324] In this embodiment, the molar ratio of Me3SiNMe2 to MoCl6 is 4.1:1; the mass ratio of MoCl6 to n-heptane is 1:10; and the molar ratio of MoCl6 to Me3SiNH t Bu is 1:2.1.

[0325] Example 4-2

[0326] The embodiment provides a preparation method of a diimino di(dimethylamino) molybdenum complex, and the preparation method comprises the following steps:

[0327] (1) under the condition of nitrogen atmosphere, 30.9 g (0.10 mol) MoCl6 reacts with 48.1 g (0.41 mol) Me3SiNMe2 in 309 g (452 mL) inert solvent n-heptane in a 1 L reaction device, after the by-product Me3SiCl no longer evaporates, the unreacted Me3SiNMe2 is distilled by heating to obtain a solution of Mo(NMe2)4Cl2;

[0328] The reaction is carried out under stirring conditions, and the stirring speed of the stirring conditions is 100 rpm; the reaction temperature is 60°C, and the reaction time is 6 h;

[0329] (2) Under the condition of nitrogen atmosphere, 27.6 g (0.21 mol) of trimethylsilyl isopropylamine Me3SiNH i Pr is added dropwise, stirring is continuously performed during the dropwise addition, ligand exchange is performed after 2 h of dropwise addition, and a product solution is obtained;

[0330] The ligand exchange is carried out under stirring conditions, and the stirring speed of the stirring conditions is 100 rpm; the ligand exchange temperature is 60°C, and the reaction time is 2 h, and then 80°C, and the reaction time is 2 h;

[0331] The obtained product solution is subjected to vacuum distillation and sublimation in a sublimator, and bis(isopropylimino)bis(dimethylamino) molybdenum complex ( i PrN=)2Mo(NMe2)2 is obtained in a second crystallization device.

[0332] In this embodiment, the molar ratio of Me3SiNMe2 to MoCl6 is 4.1:1; the mass ratio of MoCl6 to n-heptane is 1:10; and the molar ratio of MoCl6 to Me3SiNH i The molar ratio of Pr is 1:2.1.

[0333] Example 4-3

[0334] The embodiment provides a preparation method of a diimino tri(methylethylamino) molybdenum complex, and the preparation method comprises the following steps:

[0335] (1) Under the condition of nitrogen atmosphere, 30.9 g (0.10 mol) of MoCl6 is reacted with 53.8 g (0.41 mol) of Me3SiNEtMe in 309 g (440 mL) of inert solvent n-octane in a 1L reaction device, after the by-product Me3SiCl is no longer distilled out, the unreacted Me3SiNEtMe is distilled by heating, and a molybdenum chloride tetra(methylethylamino) Mo(NEtMe)4Cl2 solution is obtained;

[0336] The reaction is carried out under stirring conditions, and the stirring speed of the stirring conditions is 100 rpm; the reaction temperature is 60°C, and the reaction time is 6 h;

[0337] (2) Under the condition of nitrogen atmosphere, 27.6 g (0.21 mol) of trimethylsilyl isopropylamine Me3SiNH t Am is added dropwise, stirring is continuously performed during the dropwise addition, ligand exchange is performed after 2 h of dropwise addition, and a product solution is obtained;

[0338] The ligand exchange is carried out under stirring at a stirring speed of 100 rpm, and at a temperature of 60 °C for 2 h and then at a temperature of 80 °C for 2 h.

[0339] The obtained product solution is subjected to vacuum distillation and sublimation in a sublimator, and a bis(tert-pentyl imino) bis(methylethylamino) molybdenum complex (CMe3N=)2Mo(NEtMe)2 is obtained in a second crystallization device. t AmN=)2Mo(NEtMe)2.

[0340] In this embodiment, the molar ratio of Me3SiNEtMe to MoCl6 is 4.1:1, the mass ratio of MoCl6 to n-octane is 1:10, and the molar ratio of MoCl6 to Me3SiNH t The molar ratio of Am is 1:2.1.

[0341] Example 4-4

[0342] The embodiment provides a preparation method of an imino tris(methylethylamino) molybdenum complex, and the preparation method comprises the following steps:

[0343] (1) Under a nitrogen atmosphere, 30.9 g (0.10 mol) of MoCl6 is reacted with 53.8 g (0.41 mol) of Me3SiNEtMe in 309 g (440 mL) of an inert solvent n-octane in a 1L reaction device, and after the by-product Me3SiCl is no longer distilled out, the unreacted Me3SiNEtMe is distilled out by heating, to obtain a molybdenum chloride tetra(methylethylamino) Mo(NEtMe)4Cl2 solution;

[0344] The reaction is carried out under stirring at a stirring speed of 100 rpm, and at a temperature of 60 °C for 6 h.

[0345] (2) Under a nitrogen atmosphere, 33.0 g (0.21 mol) of trimethylsilyl cyclopentylamine Me3SiNHCp is added dropwise while stirring is continuously performed, and after 2 h of the dropwise addition, ligand exchange is performed to obtain a product solution;

[0346] The ligand exchange is carried out under stirring at a stirring speed of 100 rpm, and at a temperature of 60 °C for 2 h and then at a temperature of 80 °C for 2 h.

[0347] The obtained product solution is subjected to vacuum distillation and sublimation in a sublimator, and a bis(cyclopentyl imino) bis(dimethylethylamino) molybdenum complex (CpN=)2Mo(NEtMe)2 is obtained in a second crystallization device.

[0348] In this embodiment, the molar ratio of Me3SiNEtMe to MoCl6 in the feed was 4.1:1; the mass ratio of MoCl6 to n-octane in the feed was 1:10; and the molar ratio of MoCl6 to Me3SiNHCp in the feed was 1:2.1.

[0349] Example 4-5

[0350] This embodiment provides a method for preparing a diimino-bis-(diethylamino) molybdenum complex, which comprises the following steps:

[0351] (1) Under a nitrogen atmosphere, 30.9 g (0.10 mol) of MoCl6 was reacted with 59.6 g (0.41 mol) of Me3SiNEt2 in 309 g (429 mL) of inert solvent n-nonyl in a 1 L reaction device. After the by-product Me3SiCl was no longer evaporated, the unreacted Me3SiNEt2 was distilled by heating, to obtain a solution of tetrakis-(diethylamino) molybdenum chloride;

[0352] The reaction was carried out under stirring conditions, and the stirring speed of the stirring conditions was 100 rpm; the temperature of the reaction was 60°C, and the time was 6 h;

[0353] (2) Under a nitrogen atmosphere, the temperature was maintained at 60°C to perform dropwise addition of 36.0 g (0.21 mol) of trimethylsilyl cyclohexylamine Me3SiNHCy, and stirring was continuously performed during the dropwise addition. After 2 h of dropwise addition, ligand exchange was performed, to obtain a product solution;

[0354] The ligand exchange was carried out under stirring conditions, and the stirring speed of the stirring conditions was 100 rpm; the temperature of the ligand exchange was 60°C for 2 h, and then 80°C for 2 h;

[0355] The obtained product solution was subjected to reduced pressure distillation and sublimation in a sublimator, and di-(cyclohexylimino)-bis-(diethylamino) molybdenum complex (CyN=)2Mo(NEt2)2 was obtained in a second crystallization device.

[0356] In this embodiment, the molar ratio of Me3SiNEt2 to MoCl6 in the feed was 4.1:1; the mass ratio of MoCl6 to n-nonyl in the feed was 1:10; and the molar ratio of MoCl6 to Me3SiNHCy in the feed was 1:2.1.

[0357] The mass, yield calculated according to the feed of molybdenum halide, and HPLC purity of the prepared tris-(dialkylamino) molybdenum complex in the above embodiment were determined, and the obtained results are shown in Table 4.

[0358] Table 4

[0359] Product mass (g) Yield (%) Purity (wt%) Example 4-1 27.1 83 99.99 Example 4-2 23.9 80 99.99 Example 4-3 29.8 78 99.96 Example 4-4 28.8 76 99.94 Example 4-5 32.2 74 99.93

[0360] In summary, the preparation method and preparation apparatus provided by the present invention have the following advantages:

[0361] (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.

[0362] (2) The preparation method of the diimino di(dialkylamino) metal complex provided by the present invention is to fully dehalogenate the halide to prepare the intermediate product dialkylamino metal halide by trimethylsilyl dialkylamine, and then perform ligand exchange with trimethylsilyl monoalkylamine to prepare the product. This method is a solid-liquid reaction of halide and dehalogenating agent, which is different from the solid-solid reaction of lithium alkylamino and halide. It is easier to disperse evenly. Within the boiling point range of 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 technical route of lithium alkylamino due to the dialkylamino, and can also avoid the generation of solid waste such as lithium salt that is not easy to separate later. It facilitates product purification and the product obtained is easy to meet the purity requirements of tungsten-containing precursor materials in integrated circuit manufacturing.

[0363] 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.

[0364] (3) The reaction apparatus for preparing high-purity dialkylamino metal halides and diimino di(dialkylamino) metal complexes provided by the present invention adopts the technical route of trimethylsilyl dialkylamine, and 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 trimethylsilyl dialkylamine and solvent can also be recovered. At the same time, low-boiling-point dialkylamine and trimethyl halosilane are collected for regenerating trimethylsilyl dialkylamine.

[0365] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a diimino bis(dialkylamino) metal complex, characterized in that, The preparation method includes the following steps: (1) Under protective atmosphere conditions, in an inert solvent, the halide MX6 reacts with trimethylsilyldialkylamine Me3SiNR 1 R 2 The reaction yields M(NR) 1 R 2 The reaction equation for a 4X2 solution is as follows: MX6 + Me3SiNR 1 R 2 → M(NR1R2)4X2 + Me3SiX; (2) Trimethylsilyl monoalkylamine Me3SiNHR under protective atmosphere conditions 3 Compared with the M(NR) obtained in step (1) 1 R 2 The ligand exchange was performed using a 4X2 solution, and the product solution was purified to obtain the diimino bis(dialkylamino) metal complex (R). 3 N=)2M(NR 1 R 2 2. The reaction formula is as follows: M(NR1R2)4X2 + Me3SiNHR 3 → (R 3 N=)2M(NR 1 R 2 )2 + Me3SiX + HNR 1 R 2 ; M is a sixth subgroup element; X is a halogen; The R 1 R 2 With R 3 Each is independently an alkyl group, where N is an amino nitrogen and Me is a methyl group.

2. The preparation method according to claim 1, characterized in that, The trimethylsilyldialkylamine Me3SiNR 1 R 2 The molar ratio of the feed to halide MX6 is 4:1 to 4.2:

1.

3. The preparation method according to claim 1, characterized in that, The reaction in step (1) is carried out at a temperature of 0°C to 150°C for a time of 3 to 30 hours.

4. The preparation method according to claim 1, characterized in that, The halide MX6 and trimethylsilyl monoalkylamine Me3SiNHR 3 The molar ratio of the feed is 1:2 to 1:2.

2.

5. The preparation method according to claim 1, characterized in that, The ligand exchange in step (2) is performed at a temperature of 0°C to 150°C for a time of 2 hours to 20 hours.

6. The preparation method according to claim 1, characterized in that, The preparation method is carried out in an apparatus system, which 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 evaporator are each independently connected to the filtration unit.

7. The preparation method according to claim 6, 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; 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; 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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