Diamino dicyclopentadienyl molybdenum complex and its preparation method and application
阅读说明：本技术 二胺基二茂钼类配合物及其制备方法与应用 (Diamino dicyclopentadienyl molybdenum complex and its preparation method and application ) 是由 逄增波 江德圣 于 2020-07-16 设计创作，主要内容包括：本发明涉及一种二胺基二茂钼类配合物及其制备方法和应用。包括以下步骤：于第一溶剂中溶解五氯化钼,冷却,制备第一溶液；于第二溶剂中溶解取代的环戊二烯锂和硼氢化钠,冷却,制备第二溶液；混合第一溶液和第二溶液,搅拌2h～4h,升温至55h～75h,反应20h-18h,向反应产物中加入烷烃萃取,收集水相,过滤,向滤液中加入氯仿,搅拌8h～12h,制备双(取代的环戊二烯锂)二氯化钼；使双(取代的环戊二烯锂)二氯化钼和二烷基胺锂反应。本发明先一步合成了二氯二茂钼类配合物,然后再将其与二烷基胺锂反应,制备了二胺基二茂钼类配合物,缩短了反应步骤,降低了生产成本,保持较高的收率,更加有利于工业化生产。(The invention relates to a diamino dicyclopentadienyl molybdenum complex and a preparation method and application thereof. The method comprises the following steps: dissolving molybdenum pentachloride in a first solvent, and cooling to prepare a first solution; dissolving substituted cyclopentadiene lithium and sodium borohydride in a second solvent, and cooling to prepare a second solution; mixing the first solution and the second solution, stirring for 2-4 h, heating to 55-75 h, reacting for 20-18 h, adding alkane into the reaction product for extraction, collecting a water phase, filtering, adding chloroform into the filtrate, and stirring for 8-12 h to prepare bis (substituted cyclopentadienyl lithium) molybdenum dichloride; bis (substituted cyclopentadienyl lithium) molybdenum dichloride and lithium dialkylamine are reacted. The invention firstly synthesizes the dichloro-dicyclopentadienyl molybdenum complex in one step, and then the dichloro-dicyclopentadienyl molybdenum complex reacts with the lithium dialkyl amine to prepare the diamino-dicyclopentadienyl molybdenum complex, thereby shortening the reaction steps, reducing the production cost, keeping higher yield and being more beneficial to industrial production.)
1. The preparation method of the diamino dicyclopentadienyl molybdenum complex is characterized by comprising the following steps:
dissolving molybdenum pentachloride in a first solvent, and cooling for the first time to prepare a first solution;
dissolving substituted cyclopentadiene lithium and sodium borohydride in a second solvent, and cooling for the second time to prepare a second solution;
mixing the first solution and the second solution, stirring for 2-4 h, heating to 55-75 ℃, reacting for 20-28 h, adding alkane into a reaction product for extraction, filtering, adding chloroform into a filtrate, and stirring for 8-12 h to prepare bis (substituted cyclopentadienyl lithium) molybdenum dichloride;
reacting the bis (substituted cyclopentadienyl lithium) molybdenum dichloride and lithium dialkylamine.
2. The method for preparing diamino-molybdenum-dicyclopentadienyl complexes according to claim 1, wherein the molar ratio of the molybdenum pentachloride to the chloroform is 1: (4.0-5.0).
3. The method for preparing diamido-dimocene-molybdenum complexes as claimed in claim 1, wherein the method for preparing the substituted cyclopentadiene-lithium comprises the following steps:
mixing the substituted cyclopentadiene and n-butyl lithium in a third solvent, and reacting for 1-3 h.
4. The method of claim 3, wherein the substituted cyclopentadiene is selected from pentamethylcyclopentadiene or pentaphenylcyclopentadiene; and/or the presence of a catalyst in the reaction mixture,
the molar ratio of the substituted cyclopentadiene to the n-butyllithium is 1 (1.0-1.1); and/or the presence of a catalyst in the reaction mixture,
the third solvent is n-hexane.
5. The method of claim 1, wherein the lithium dialkylamine is selected from lithium dimethylamine, lithium diethylamine or lithium methylethylamine.
6. A process for preparing a diaminodicyclopentadienyl molybdenum-based complex as claimed in claim 5, wherein the step of reacting said bis (substituted cyclopentadienyl lithium) molybdenum dichloride and lithium dialkylamine comprises:
dissolving bis (substituted cyclopentadienyl lithium) molybdenum dichloride in a fourth solvent, dropwise adding lithium dialkylamine, and stirring for 8-12 h.
7. The method for preparing a diaminodicyclopentadienyl molybdenum complex according to claim 6, wherein the molar ratio of the bis (substituted cyclopentadienyl lithium) molybdenum dichloride and the lithium dialkylamine is 1 (1.8-2.2); and/or the presence of a catalyst in the reaction mixture,
the fourth solvent is methyl tert-butyl ether.
8. A diamino dicyclopentadienyl molybdenum complex is characterized by having a structure shown in a formula (1):
wherein R is1Represents a substituent group, R2–R3Each independently selected from alkyl;
the preparation method of the diamino molybdenum dicyclopentadienyl complex comprises the following steps:
dissolving molybdenum pentachloride in a first solvent, and cooling for the first time to prepare a first solution;
dissolving substituted cyclopentadiene lithium and sodium borohydride in a second solvent, and cooling for the second time to prepare a second solution;
mixing the first solution and the second solution, stirring for 2-4 h, heating to 55-75 ℃, reacting for 20-28 h, adding alkane into a reaction product for extraction, filtering, adding chloroform into a filtrate, and stirring for 8-12 h to prepare bis (substituted cyclopentadienyl lithium) molybdenum dichloride;
reacting the bis (substituted cyclopentadienyl lithium) molybdenum dichloride and lithium dialkylamine.
9. The molybdenum diamido-dicyclopentadienyl complex as claimed in claim 8, wherein R is selected from the group consisting of1Is methyl or phenyl; the R is2–R3Each independently selected from methyl or ethyl.
10. A molybdenum sulfide thin film produced from the production method according to any one of claims 1 to 7 or the diamido-dicyclopentadienyl molybdenum complex according to claim 8 or 9.
Technical Field
The invention relates to the technical field of organic chemistry, in particular to a diamino dicyclopentadienyl molybdenum complex and a preparation method and application thereof.
Background
Two-dimensional layered Transition Metal Sulfides (TMDs) have a graphene-like structure, and are widely considered as one of star materials with great potential for future application in electronic devices due to unique high electron mobility, excellent optical absorption, quantum Hall effect and other excellent performances. Wherein molybdenum sulfide (MoS)2) The film is similar in structure and performance toGraphene, but unlike zero band gap graphene films, molybdenum disulfide has a tunable band gap. The band gap of the blocky crystal molybdenum disulfide is 1.2eV, the electron transition mode is indirect transition, the band gap of the single-layer molybdenum disulfide can reach 1.8eV, and the electron transition mode is direct transition. Therefore, the molybdenum disulfide film has a unique structure, excellent physical properties, an adjustable band gap and relatively high carrier mobility, so that the molybdenum disulfide film becomes a two-dimensional nano material with great application potential in the fields of electricity, optics, semiconductors and the like.
Many methods for preparing MoS have been reported2The thin film may be formed by mechanical stripping, chemical stripping, gas-solid growth, Chemical Vapor Deposition (CVD), or the like. However, the conventional method has the problems of high cost, difficulty in controlling the thickness, high deposition temperature, more uncontrollable parameters and the like, and limits the MoS2The use of (1). Furthermore, large-area single crystal MoS2The preparation of atomic layer thin films is still the current restriction of MoS2The bottleneck of the application of thin films in high performance electronics. Atomic Layer Deposition (ALD) is gaining increasing attention due to its self-limiting nature and excellent three-dimensional structure conformality. In recent years, molybdenum hexacarbonyl (Mo (CO))6) Solid molybdenum source and dimethyl disulfide (C)2H6S2) A gaseous sulfur source, and the atomic layer deposition technology is adopted to obtain high-purity MoS2Report on films [ CN107937884A]Therefore, it is of great importance to develop a source material which has a high saturated vapor pressure and is easily and stably synthesized.
The applicant has reported a tungsten complex and a process for its preparation (application No. CN 202010249921.7). In this report, tungsten hexachloride is first reacted with cyclopentene and ethylene glycol dimethyl ether to prepare a tungsten tetrachloride ethylene glycol dimethyl ether adduct, which is then reacted with cyclopentadienyl lithium to obtain a bis (cyclopentadienyl lithium) tungsten dichloride intermediate. The cyclopentene is used as a low-boiling point reducing agent (the boiling point is 44-46 ℃) and needs to be stored at low temperature, which puts higher requirements on industrial production of the process route, and the preparation method of the molybdenum complex is different from that of the tungsten complex. Therefore, it is necessary to continue to investigate the synthesis process of the molybdenum complex.
Disclosure of Invention
Based on the above, the invention provides a preparation method of diamino cyclopentadienyl molybdenum complex, which adopts different synthesis routes and adopts a one-pot method to mix, so as to synthesize the dichloro cyclopentadienyl molybdenum complex in one step, and then the dichloro cyclopentadienyl molybdenum complex reacts with lithium dialkyl amine to prepare the diamino cyclopentadienyl molybdenum complex, thereby shortening the reaction steps, reducing the production cost, simultaneously keeping higher yield and being more beneficial to industrial production.
The technical scheme of the invention is as follows:
a preparation method of diamino molybdenum dicyclopentadienyl complexes comprises the following steps:
dissolving molybdenum pentachloride in a first solvent, and cooling for the first time to prepare a first solution;
dissolving substituted cyclopentadiene lithium and sodium borohydride in a second solvent, and cooling for the second time to prepare a second solution;
mixing the first solution and the second solution, stirring for 2-4 h, heating to 55-75 ℃, reacting for 20-28 h, adding alkane into a reaction product for extraction, filtering, adding chloroform into a filtrate, and stirring for 8-12 h to prepare bis (substituted cyclopentadienyl lithium) molybdenum dichloride;
reacting the bis (substituted cyclopentadienyl lithium) molybdenum dichloride and lithium dialkylamine.
In one preferred embodiment, the molar ratio of molybdenum pentachloride to chloroform is 1: (4.0-5.0).
In one preferred embodiment, the method for preparing the substituted cyclopentadienyl lithium comprises the following steps:
mixing the substituted cyclopentadiene and n-butyl lithium in a third solvent, and reacting for 1-3 h.
In one preferred embodiment, the substituted cyclopentadiene is selected from pentamethylcyclopentadiene or pentaphenylcyclopentadiene.
In one preferred embodiment, the molar ratio of the substituted cyclopentadiene to the n-butyllithium is 1 (1.0-1.1).
In one preferred embodiment, the third solvent is n-hexane.
In one preferred embodiment, the lithium dialkylamine is selected from lithium dimethylamine, lithium diethylamine or lithium methylethylamine.
In one preferred embodiment, the step of reacting the bis (substituted cyclopentadienyl lithium) molybdenum dichloride and lithium dialkylamine comprises:
dissolving bis (substituted cyclopentadienyl lithium) molybdenum dichloride in a fourth solvent, dropwise adding lithium dialkylamine, and stirring for 8-12 h.
In one preferred embodiment, the molar ratio of the bis (substituted cyclopentadienyl lithium) molybdenum dichloride and the lithium dialkylamine is 1 (1.8-2.2).
In one preferred embodiment, the fourth solvent is methyl tert-butyl ether.
In one preferred embodiment, the first cooling is to a temperature of-10 ℃ to 10 ℃.
In one preferred embodiment, the second cooling is to a temperature of-10 ℃ to 10 ℃.
In one preferred embodiment, the molar ratio of molybdenum pentachloride, substituted lithium cyclopentadienide and sodium borohydride is 1: (2.0-3.0): (2.0-3.0).
In one preferred embodiment, the first solvent is a mixed solvent of toluene and tetrahydrofuran.
In one preferred embodiment, the second solvent is tetrahydrofuran.
In one preferred embodiment, the alkane is selected from n-hexane or n-pentane.
The invention also provides a diamino molybdenum dicyclopentadienyl complex.
The technical scheme is as follows:
a diamino molybdenum dicyclopentadienyl complex has a structure shown in a formula (1):
wherein R is1Represents a substituent group, R2–R3Each independently selected from alkyl;
the preparation method of the diamino molybdenum dicyclopentadienyl complex comprises the following steps:
dissolving molybdenum pentachloride in a first solvent, and cooling for the first time to prepare a first solution;
dissolving substituted cyclopentadiene lithium and sodium borohydride in a second solvent, and cooling for the second time to prepare a second solution;
mixing the first solution and the second solution, stirring for 2-4 h, heating to 55-75 ℃, reacting for 20-28 h, adding alkane into a reaction product for extraction, filtering, adding chloroform into a filtrate, and stirring for 8-12 h to prepare bis (substituted cyclopentadienyl lithium) molybdenum dichloride;
reacting the bis (substituted cyclopentadienyl lithium) molybdenum dichloride and lithium dialkylamine.
In one preferred embodiment, R is1Is methyl or phenyl; the R is2–R3Each independently selected from methyl or ethyl.
The invention also provides a molybdenum sulfide film.
The technical scheme is as follows:
the preparation raw materials of the molybdenum sulfide film comprise the diamino dicyclopentadienyl molybdenum complex prepared by the preparation method or the diamino dicyclopentadienyl molybdenum complex.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes molybdenum pentachloride, substituted cyclopentadiene lithium, sodium borohydride and chloroform as raw materials, adopts a one-pot method to mix, synthesizes dichlorometallocene molybdenum complexes in one step, and then reacts the dichlorometallocene molybdenum complexes with lithium dialkylamine to prepare the diamido metallocene molybdenum complexes, the reaction steps are few, and compared with the use of cyclopentene, the reaction reagent has stable property, stable storage and easy obtaining. Meanwhile, each reactant is cheap, the cost is reduced, the reaction process is relatively mild, potential safety hazards are avoided, the safety of operators is guaranteed, higher yield can be kept, and the industrial production is facilitated. The diamino dicyclopentadienyl molybdenum complex prepared by the invention can obtain a molybdenum-containing film with nanometer thickness by an atomic layer deposition method, especially a molybdenum sulfide film with higher quality, and has important scientific research value and wide industrial prospect.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the complexes of the invention, when any variable (e.g. R)1，R2Etc.) more than one time in any component, then the definition at each occurrence is independent of the definitions at every other occurrence. Also, combinations of substituents and variables are permissible only if such combinations result in stable compounds.
In the complex of the present invention, "substituted" means that the atom in the substituent is substituted with a substituent.
In the complex of the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a fused ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
The invention provides a preparation method of diamido-dimocene molybdenum complexes, which adopts a one-pot method for mixing to synthesize dichloro-dimocene molybdenum complexes in one step, and then the dichloro-dimocene molybdenum complexes react with lithium dialkyl amine to prepare the diamido-dimocene molybdenum complexes. The technical scheme is as follows:
a preparation method of diamino molybdenum dicyclopentadienyl complexes comprises the following steps:
dissolving molybdenum pentachloride in a first solvent, and cooling for the first time to prepare a first solution;
dissolving substituted cyclopentadiene lithium and sodium borohydride in a second solvent, and cooling for the second time to prepare a second solution;
mixing the first solution and the second solution, stirring for 2-4 h, heating to 55-75 ℃, reacting for 20-28 h, adding alkane into a reaction product for extraction, filtering, adding chloroform into a filtrate, and stirring for 8-12 h to prepare bis (substituted cyclopentadienyl lithium) molybdenum dichloride;
reacting the bis (substituted cyclopentadienyl lithium) molybdenum dichloride and lithium dialkylamine.
Specifically, the above reaction of the present invention can be carried out in a reaction vessel protected by an inert atmosphere. Further, the inert atmosphere may be a high purity nitrogen or high purity argon atmosphere.
The first solvent, the second solvent and the alkane can be subjected to water removal and oxygen removal treatment.
Preferably, the first solvent is a mixture of tetrahydrofuran and toluene, and the molybdenum pentachloride is dissolved in the mixture of tetrahydrofuran and toluene.
The first solution is cooled, in one preferred embodiment to a temperature of-10 ℃ to 10 ℃.
Preferably, the second solvent is tetrahydrofuran in which the substituted lithium cyclopentadienide and sodium borohydride are dissolved.
Cooling the second solution, wherein in a preferred embodiment, the second cooling is performed to a temperature of-10 ℃ to 10 ℃.
The preparation method of the substituted cyclopentadiene lithium can comprise the following steps:
mixing the substituted cyclopentadiene and n-butyl lithium in a third solvent, and reacting for 1-3 h.
Preferably, the third solvent is n-hexane.
It can be understood that n-hexane solution of n-butyllithium can be added dropwise to n-hexane solution of cyclopentadiene at-5 deg.C to 5 deg.C, and then the reaction is allowed to return to room temperature for 1h to 3 h. After the reaction is finished, the product can be washed and dried to prepare the substituted cyclopentadiene lithium.
Preferably, the substituted cyclopentadiene is selected from pentamethylcyclopentadiene or pentaphenylcyclopentadiene. Correspondingly, the substituted cyclopentadienyl lithium is selected from pentamethylcyclopentadienyl lithium or pentaphenylcyclopentadienyl lithium.
Preferably, the molar ratio of the substituted cyclopentadiene to the n-butyllithium is 1 (1.0-1.1).
In a preferred embodiment, the molar ratio of molybdenum pentachloride, substituted lithium cyclopentadienide and sodium borohydride is 1: (2.0-3.0): (2.0-3.0).
Because the sodium borohydride generally releases heat and generates hydrogen when participating in the reaction, the first solution can be dropwise added into the second solution at the temperature of-10 ℃ in consideration of the safety of the system, after the dropwise addition is finished, in order to improve the reaction yield, the stirring can be firstly restored at room temperature for 2-4 h, after the reaction is stable, the temperature is raised to 55-75 ℃, and the reaction is carried out for 20-28 h. And after the reaction is finished, decompressing and draining the solvent to obtain a reaction product, adding alkane into the reaction product for extraction, filtering, adding chloroform into the filtrate, stirring for 8-12 h, filtering, washing the solid, and drying to obtain the molybdenum dichlorometallocenes complex.
In a preferred embodiment, the alkane is selected from n-hexane or n-pentane.
The molar ratio of the molybdenum pentachloride to the chloroform is 1: (4.0 to 5.0) and the yield is higher at the molar ratio.
Compared with dichloromethane or other chlorine substitution reagents capable of converting dihydrodicyclopentadienyl tungsten into dichlorodicyclopentadienyl tungsten, the method for preparing the dichlorodicyclopentadienyl molybdenum complex by using chloroform has higher yield in the process route of the application.
In a preferred embodiment, the lithium dialkylamine is selected from lithium dimethylamine, lithium diethylamine or lithium methylethylamine.
It will be appreciated that the step of reacting the bis (substituted cyclopentadienyl lithium) molybdenum dichloride and lithium dialkylamine comprises:
dissolving bis (substituted cyclopentadienyl lithium) molybdenum dichloride in a fourth solvent, dropwise adding lithium dialkylamine, and stirring for 8-12 h.
Preferably, the fourth solvent is methyl tert-butyl ether.
It is understood that lithium dialkylamine is slowly added dropwise to a solution of bis (substituted cyclopentadienyl lithium) molybdenum dichloride in methyl tert-butyl ether at-5 ℃ to 5 ℃ with stirring, and after the addition is complete, stirring is resumed at room temperature for 8h to 12 h. And after the reaction is finished, decompressing and draining the solvent, adding alkane into the reaction product for extraction, filtering, and draining the solvent from the filtrate to obtain the diamino dicyclopentadienyl molybdenum complex.
Preferably, the molar ratio of the bis (substituted cyclopentadienyl lithium) molybdenum dichloride to the lithium dialkylamine is 1 (1.8-2.2).
The method has fewer reaction steps, and compared with the method using cyclopentene, the method has the advantages of stable reaction reagent property, stable storage and easy obtaining. Meanwhile, each reactant is cheap, the cost is reduced, the reaction process is relatively mild, potential safety hazards are avoided, the safety of operators is guaranteed, higher yield can be kept, and the industrial production is facilitated.
The invention also provides a diamino molybdenum dicyclopentadienyl complex.
The technical scheme is as follows:
a diamino molybdenum dicyclopentadienyl complex has a structure shown in a formula (1):
wherein R is1Represents a substituent group, R2–R3Each independently selected from alkyl;
the preparation method of the diamino molybdenum dicyclopentadienyl complex comprises the following steps:
dissolving molybdenum pentachloride in a first solvent, and cooling for the first time to prepare a first solution;
dissolving substituted cyclopentadiene lithium and sodium borohydride in a second solvent, and cooling for the second time to prepare a second solution;
mixing the first solution and the second solution, stirring for 2-4 h, heating to 55-75 ℃, reacting for 20-28 h, adding alkane into a reaction product for extraction, filtering, adding chloroform into a filtrate, and stirring for 8-12 h to prepare bis (substituted cyclopentadienyl lithium) molybdenum dichloride;
reacting the bis (substituted cyclopentadienyl lithium) molybdenum dichloride and lithium dialkylamine.
In one preferred embodiment, R is1Is methyl or phenyl; the R is2–R3Each independently selected from methyl or ethyl.
The diamino dicyclopentadienyl molybdenum complex can be used for obtaining a molybdenum sulfide film by an atomic layer deposition method.
The invention also provides a molybdenum sulfide film.
The technical scheme is as follows:
the preparation raw materials of the molybdenum sulfide film comprise the diamino dicyclopentadienyl molybdenum complex prepared by the preparation method or the diamino dicyclopentadienyl molybdenum complex.
The following examples and comparative examples are further described below, and the starting materials used in the following examples can be commercially available, unless otherwise specified, and the equipment used therein can be commercially available, unless otherwise specified.
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