CN111747994A - Diamino dicyclopentadienyl molybdenum complex and its preparation method and application - Google Patents
Diamino dicyclopentadienyl molybdenum complex and its preparation method and application Download PDFInfo
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- -1 Diamino dicyclopentadienyl molybdenum Chemical compound 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 65
- 238000003756 stirring Methods 0.000 claims abstract description 51
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000000605 extraction Methods 0.000 claims abstract description 29
- 239000000706 filtrate Substances 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 24
- 239000012279 sodium borohydride Chemical class 0.000 claims abstract description 22
- 229910000033 sodium borohydride Chemical class 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 12
- FLILUVGNNJPQAV-UHFFFAOYSA-N cyclopenta-1,3-diene;lithium Chemical class [Li].C1C=CC=C1 FLILUVGNNJPQAV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 147
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical class [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 34
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical group COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 25
- 229910052750 molybdenum Inorganic materials 0.000 claims description 22
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 20
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 14
- OLUQNHZGDAZRKM-UHFFFAOYSA-N [Li].CNC Chemical group [Li].CNC OLUQNHZGDAZRKM-UHFFFAOYSA-N 0.000 claims description 13
- 239000011733 molybdenum Substances 0.000 claims description 12
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical group CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- BMRASELKGKHCIX-UHFFFAOYSA-N lithium;n-methylethanamine Chemical compound [Li].CCNC BMRASELKGKHCIX-UHFFFAOYSA-N 0.000 claims description 7
- NCFSDGWPAKOPOU-UHFFFAOYSA-N n-ethylethanamine;lithium Chemical compound [Li].CCNCC NCFSDGWPAKOPOU-UHFFFAOYSA-N 0.000 claims description 7
- YGLVWOUNCXBPJF-UHFFFAOYSA-N (2,3,4,5-tetraphenylcyclopenta-1,4-dien-1-yl)benzene Chemical compound C1=CC=CC=C1C1C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 YGLVWOUNCXBPJF-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims 3
- 239000011541 reaction mixture Substances 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 238000009776 industrial production Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- YQZUTDPJTAZPQJ-UHFFFAOYSA-L cyclopentane;dichloromolybdenum Chemical compound Cl[Mo]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 YQZUTDPJTAZPQJ-UHFFFAOYSA-L 0.000 abstract description 3
- 238000004904 shortening Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- QEKDVHNXEFFHLF-UHFFFAOYSA-N lithium;1,2,3,4,5-pentamethylcyclopentane Chemical group [Li].C[C]1[C](C)[C](C)[C](C)[C]1C QEKDVHNXEFFHLF-UHFFFAOYSA-N 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- BOKPGVUZZHWQHL-UHFFFAOYSA-L CC1=C(C(=C(C1(C)[Mo](Cl)(Cl)C1(C(=C(C(=C1C)C)C)C)C)C)C)C Chemical compound CC1=C(C(=C(C1(C)[Mo](Cl)(Cl)C1(C(=C(C(=C1C)C)C)C)C)C)C)C BOKPGVUZZHWQHL-UHFFFAOYSA-L 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 239000010408 film Substances 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002751 molybdenum Chemical class 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- DBKDYYFPDRPMPE-UHFFFAOYSA-N lithium;cyclopenta-1,3-diene Chemical compound [Li+].C=1C=C[CH-]C=1 DBKDYYFPDRPMPE-UHFFFAOYSA-N 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000000231 atomic layer deposition Methods 0.000 description 5
- 125000006413 ring segment Chemical group 0.000 description 5
- FHZTUGIHKLLROO-UHFFFAOYSA-N C1(=CC=CC=C1)C1=C(C(=C(C1([Li])C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C1=C(C(=C(C1([Li])C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 FHZTUGIHKLLROO-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052961 molybdenite Inorganic materials 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- YDKGOSREOOSMDW-UHFFFAOYSA-N N[Mo]N Chemical compound N[Mo]N YDKGOSREOOSMDW-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKLQFFLQJUXTAD-UHFFFAOYSA-L Cl[Mo](Cl)C1C=CC=C1 Chemical compound Cl[Mo](Cl)C1C=CC=C1 OKLQFFLQJUXTAD-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UJJGAPWIHDJEHM-UHFFFAOYSA-J Cl[W](Cl)(Cl)Cl.COCCOC Chemical compound Cl[W](Cl)(Cl)Cl.COCCOC UJJGAPWIHDJEHM-UHFFFAOYSA-J 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZQMQKQFAGANRGQ-UHFFFAOYSA-L [W](Cl)Cl.C1(C=CC=C1)[Li].C1(C=CC=C1)[Li] Chemical compound [W](Cl)Cl.C1(C=CC=C1)[Li].C1(C=CC=C1)[Li] ZQMQKQFAGANRGQ-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001717 carbocyclic compounds Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- GXMZHFAZTNJTEW-UHFFFAOYSA-L cyclopentane;dichlorotungsten Chemical compound Cl[W]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 GXMZHFAZTNJTEW-UHFFFAOYSA-L 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
Abstract
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.
Description
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.
Example 1
The embodiment provides a diamino molybdenum metallocene complex and a preparation method thereof, which are carried out in a reaction container protected by a high-purity argon atmosphere, and the preparation method comprises the following specific steps:
step 1: 50 g (0.367mol) of pentamethylcyclopentadiene and 50 ml of n-hexane were added to a 500 ml Schlenk bottle under an argon atmosphere to lower the temperature of the system to 0 ℃ and 147 ml of an n-hexane solution of n-butyllithium was added dropwise thereto at a concentration of 2.5 mol/l. After the dropwise addition, the room temperature is recovered and the reaction is carried out for 2 hours, the filtration is carried out, the normal hexane is used for washing and drying, 41 g of pentamethylcyclopentadienyl lithium is obtained, and the yield is 80%;
step 2: 10 g (0.037mol) of molybdenum pentachloride, 25 ml of toluene and 125 ml of tetrahydrofuran are sequentially added into a 250 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a first solution. 11 g (0.077mol) of pentamethylcyclopentadienyl lithium prepared in the step 1, 4 g (0.106mol) of sodium borohydride and 375 ml of tetrahydrofuran are sequentially added into a 500 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a second solution. At the temperature of minus 10 ℃, dropwise adding the first solution into the second solution, recovering to room temperature after dropwise adding, stirring at room temperature for 3 hours, heating to 65 ℃, heating for 24 hours, carrying out vacuum pumping on the solvent, adding 400 ml of n-hexane for extraction, passing through diatomite, concentrating the filtrate to 250 ml, adding 13 ml (0.161mol) of chloroform, stirring at room temperature for 10 hours, filtering, washing the solid with n-hexane, and carrying out vacuum drying to obtain 12 g of bis (pentamethylcyclopentadienyl) molybdenum dichloride with the yield of 80%;
and step 3: 40 g (0.092mol) of bis (pentamethylcyclopentadienyl) molybdenum dichloride prepared in step 2 and 300 ml of methyl tert-butyl ether were successively charged into a 500 ml Schlenk flask, cooled to 0 ℃ and stirred at room temperature for 10 hours after 9 g (0.177mol) of lithium dimethylamine was slowly added with stirring. Then, the solvent is pumped out under reduced pressure, n-hexane is added for extraction, diatomite is added, the solvent n-hexane is pumped out from the filtrate, and 33 g of bis (dimethylamino) bis (pentamethylcyclopentadienyl) molybdenum product is obtained, wherein the yield is 80%.
The element analysis and detection of the bis (dimethylamino) bis (pentamethylcyclopentadienyl) molybdenum prepared in the example have the following theoretical values: C63.4H: 9.3, N6.2, Mo 21.1, found: 62.6 percent of C, 9.6 percent of H, 6.8 percent of N and 21.3 percent of Mo.
Example 2
The embodiment provides a diamino molybdenum dicyclopentadienyl complex and a preparation method thereof, and the preparation method comprises the following specific steps:
step 1: 80 g (0.179mol) of pentaphenylcyclopentadiene and 100 ml of n-hexane were added to a 500 ml Schlenk bottle under a nitrogen atmosphere, the temperature of the system was lowered to 0 ℃ and 72 ml of an n-hexane solution of n-butyllithium was added dropwise at a concentration of 2.5 mol/l. After the dropwise addition, the room temperature is recovered and the reaction is carried out for 2 hours, the reaction product is filtered, washed by n-hexane and dried to obtain 70 g of pentamethylcyclopentadienyl lithium with the yield of 86%;
step 2: 22 g (0.081mol) of molybdenum pentachloride, 60 ml of toluene and 250 ml of tetrahydrofuran are sequentially added into a 500 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a first solution. 38 g (0.084mol) of the pentaphenylcyclopentadienyl lithium prepared in the step 1, 8 g (0.211mol) of sodium borohydride and 500 ml of tetrahydrofuran are sequentially added into a 2000 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a second solution. At the temperature of minus 10 ℃, dropwise adding the first solution into the second solution, recovering to room temperature after dropwise adding, stirring at room temperature for 3 hours, heating to 65 ℃, heating for 24 hours, carrying out vacuum drying on the solvent, adding 1000 ml of n-hexane for extraction, passing through diatomite, concentrating the filtrate to 500 ml, adding 30 ml (0.372mol) of chloroform, stirring at room temperature for 10 hours, filtering, washing the solid with n-hexane, and carrying out vacuum drying to obtain 67 g of bis (pentaphenylcyclopentadienyl) molybdenum dichloride with the yield of 79%;
and step 3: to a 500 ml Schlenk flask were added 50 g (0.047mol) of bis (pentaphenylcyclopentadienyl) molybdenum dichloride prepared in step 2 and 300 ml of methyl t-butyl ether in this order, and then cooled to 0 ℃ and, after slowly adding 5 g (0.098mol) of lithium dimethylamine with stirring, stirred at room temperature for 10 hours. Then, the solvent is pumped out under reduced pressure, n-hexane is added for extraction, diatomite is filtered, the solvent n-hexane is pumped out from the filtrate, and 43 g of bis (dimethylamino) bis (pentaphenylcyclopentadienyl) molybdenum product is obtained, wherein the yield is 85%.
The bis (dimethylamino) bis (pentaphenylcyclopentadienyl) molybdenum prepared in the example was subjected to elemental analysis and detection, and the theoretical value was: C82.7H: 5.8, N:2.6, Mo:8.9, measurement: 81.8 percent of C, 6.3 percent of H, 2.3 percent of N and 9.3 percent of Mo.
Example 3
This example provides a diamino-dimocene-molybdenum complex and a method for preparing the same, which is substantially the same as the method in example 1, except that, in step 3, 9 g (0.177mol) of dimethylamine lithium is replaced by 14 g (0.177mol) of diethylamine lithium, and finally a bis (diethylamino) bis (pentamethylcyclopentadienyl) molybdenum product is prepared, specifically including the following steps:
step 1: 50 g (0.367mol) of pentamethylcyclopentadiene and 50 ml of n-hexane were added to a 500 ml Schlenk bottle under an argon atmosphere to lower the temperature of the system to 0 ℃ and 147 ml of an n-hexane solution of n-butyllithium was added dropwise thereto at a concentration of 2.5 mol/l. After the dropwise addition, the room temperature is recovered and the reaction is carried out for 2 hours, the filtration is carried out, the normal hexane is used for washing and drying, 41 g of pentamethylcyclopentadienyl lithium is obtained, and the yield is 80%;
step 2: 10 g (0.037mol) of molybdenum pentachloride, 25 ml of toluene and 125 ml of tetrahydrofuran are sequentially added into a 250 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a first solution. 11 g (0.077mol) of pentamethylcyclopentadienyl lithium prepared in the step 1, 4 g (0.106mol) of sodium borohydride and 375 ml of tetrahydrofuran are sequentially added into a 500 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a second solution. At the temperature of minus 10 ℃, dropwise adding the first solution into the second solution, recovering to room temperature after dropwise adding, stirring at room temperature for 3 hours, heating to 65 ℃, heating for 24 hours, carrying out vacuum pumping on the solvent, adding 400 ml of n-hexane for extraction, passing through diatomite, concentrating the filtrate to 250 ml, adding 13 ml (0.161mol) of chloroform, stirring at room temperature for 10 hours, filtering, washing the solid with n-hexane, and carrying out vacuum drying to obtain 12 g of bis (pentamethylcyclopentadienyl) molybdenum dichloride with the yield of 80%;
and step 3: 40 g (0.092mol) of bis (pentamethylcyclopentadienyl) molybdenum dichloride prepared in step 2 and 300 ml of methyl tert-butyl ether were successively charged into a 500 ml Schlenk flask, cooled to 0 ℃ and stirred at room temperature for 10 hours after 14 g (0.177mol) of lithium diethylamine was slowly added with stirring. Then, the solvent was drained under reduced pressure, n-hexane was added for extraction, celite was added, and the solvent n-hexane was drained from the filtrate to obtain 38 g of bis (diethylamino) bis (pentamethylcyclopentadienyl) molybdenum, with a yield of 81%.
The element analysis and detection of the bis (diethylamino) bis (pentamethylcyclopentadienyl) molybdenum prepared in the example have the following theoretical values: 65.9C, 9.9H, 5.5N, 18.8 Mo, measured values: 66.3 percent of C, 10.3 percent of H, 6.1 percent of N and 19.2 percent of Mo.
Example 4
This example provides a diamino-dimocene-molybdenum complex and its preparation method, which is substantially the same as the method of example 1 except that, in step 3, 9 g (0.177mol) of dimethylamine lithium is replaced by 11.5 g (0.177mol) of methylethylamine lithium to obtain the final product bis (methylethylamino) bis (pentamethylcyclopentadienyl) molybdenum, and the specific steps are as follows:
step 1: 50 g (0.367mol) of pentamethylcyclopentadiene and 50 ml of n-hexane were added to a 500 ml Schlenk bottle under an argon atmosphere to lower the temperature of the system to 0 ℃ and 147 ml of an n-hexane solution of n-butyllithium was added dropwise thereto at a concentration of 2.5 mol/l. After the dropwise addition, the room temperature is recovered and the reaction is carried out for 2 hours, the filtration is carried out, the normal hexane is used for washing and drying, 41 g of pentamethylcyclopentadienyl lithium is obtained, and the yield is 80%;
step 2: 10 g (0.037mol) of molybdenum pentachloride, 25 ml of toluene and 125 ml of tetrahydrofuran are sequentially added into a 250 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a first solution. 11 g (0.077mol) of pentamethylcyclopentadienyl lithium prepared in the step 1, 4 g (0.106mol) of sodium borohydride and 375 ml of tetrahydrofuran are sequentially added into a 500 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a second solution. At the temperature of minus 10 ℃, dropwise adding the first solution into the second solution, recovering to room temperature after dropwise adding, stirring at room temperature for 3 hours, heating to 65 ℃, heating for 24 hours, carrying out vacuum pumping on the solvent, adding 400 ml of n-hexane for extraction, passing through diatomite, concentrating the filtrate to 250 ml, adding 13 ml (0.161mol) of chloroform, stirring at room temperature for 10 hours, filtering, washing the solid with n-hexane, and carrying out vacuum drying to obtain 12 g of bis (pentamethylcyclopentadienyl) molybdenum dichloride with the yield of 80%;
and step 3: 40 g (0.092mol) of bis (pentamethylcyclopentadienyl) molybdenum dichloride prepared in step 2 and 300 ml of methyl tert-butyl ether were sequentially added to a 500 ml Schlenk flask, cooled to 0 ℃ and stirred at room temperature for 10 hours after 11.5 g (0.177mol) of lithium methylethylamine was slowly added thereto with stirring. Then, the solvent is pumped out under reduced pressure, n-hexane is added for extraction, diatomite is added, the solvent n-hexane is pumped out from the filtrate, and 38 g of bis (methylethylamino) bis (pentamethylcyclopentadienyl) molybdenum product is obtained, wherein the yield is 86%.
The element analysis and detection are carried out on the bis (methylethylamino) bis (pentamethylcyclopentadienyl) molybdenum prepared in the embodiment, and the theoretical value is as follows: c:64.7, H:9.6, N:5.8, Mo:19.9, measurement: 65.3 percent of C, 10.3 percent of H, 6.2 percent of N and 19.1 percent of Mo.
Example 5
This example provides a diamino-dimolybdenum complex and its preparation method, which is substantially the same as the method of example 2, except that, in step 3, 5 g (0.098mol) of dimethylamine lithium is replaced by 7.7 g (0.098mol) of diethylamine lithium, and the final product bis (diethylamino) bis (pentaphenylcyclopentadienyl) molybdenum is prepared by the following steps:
step 1: 80 g (0.179mol) of pentaphenylcyclopentadiene and 100 ml of n-hexane were added to a 500 ml Schlenk bottle under an argon atmosphere to lower the temperature of the system to 0 ℃ and 72 ml of an n-hexane solution of n-butyllithium was added dropwise thereto at a concentration of 2.5 mol/l. After the dropwise addition, the room temperature is recovered and the reaction is carried out for 2 hours, the reaction product is filtered, washed by n-hexane and dried to obtain 70 g of pentamethylcyclopentadienyl lithium with the yield of 86%;
step 2: 22 g (0.081mol) of molybdenum pentachloride, 60 ml of toluene and 250 ml of tetrahydrofuran are sequentially added into a 500 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a first solution. 38 g (0.084mol) of the pentaphenylcyclopentadienyl lithium prepared in the step 1, 8 g (0.211mol) of sodium borohydride and 500 ml of tetrahydrofuran are sequentially added into a 2000 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a second solution. At the temperature of minus 10 ℃, dropwise adding the first solution into the second solution, recovering to room temperature after dropwise adding, stirring at room temperature for 3 hours, heating to 65 ℃, heating for 24 hours, carrying out vacuum drying on the solvent, adding 1000 ml of n-hexane for extraction, passing through diatomite, concentrating the filtrate to 500 ml, adding 30 ml (0.372mol) of chloroform, stirring at room temperature for 10 hours, filtering, washing the solid with n-hexane, and carrying out vacuum drying to obtain 67 g of bis (pentaphenylcyclopentadienyl) molybdenum dichloride with the yield of 79%;
and step 3: to a 500 ml Schlenk flask were added 50 g (0.047mol) of bis (pentaphenylcyclopentadienyl) molybdenum dichloride prepared in step 2 and 300 ml of methyl t-butyl ether in this order, and then cooled to 0 ℃ and, while stirring, 7.7 g (0.098mol) of lithium diethylamine was slowly added and then stirred at room temperature for 10 hours. Then, the solvent was drained under reduced pressure, n-hexane was added for extraction, celite was added, and the solvent n-hexane was drained from the filtrate to obtain 43 g of bis (diethylamino) bis (pentaphenylcyclopentadienyl) molybdenum product with a yield of 80%.
The bis (diethylamino) bis (pentaphenylcyclopentadienyl) molybdenum prepared in this example was subjected to elemental analysis and detection, and the theoretical value was: 82.8C, 6.2H, 2.5N, 8.5 Mo, measurement: 83.3 percent of C, 6.3 percent of H, 3.2 percent of N and 8.1 percent of Mo.
Example 6
This example provides a diamino-dimocene-molybdenum complex and its preparation method, which is substantially the same as the method of example 2, except that, in step 3, 5 g (0.098mol) of dimethylamine lithium is replaced by 6.4 g (0.0948mol) of methylethylamine lithium, and the final product bis (methylethylamino) bis (pentaphenylcyclopentadienyl) molybdenum is prepared by the following steps:
step 1: 80 g (0.179mol) of pentaphenylcyclopentadiene and 100 ml of n-hexane were added to a 500 ml Schlenk bottle under an argon atmosphere to lower the temperature of the system to 0 ℃ and 72 ml of an n-hexane solution of n-butyllithium was added dropwise thereto at a concentration of 2.5 mol/l. After the dropwise addition, the room temperature is recovered and the reaction is carried out for 2 hours, the reaction product is filtered, washed by n-hexane and dried to obtain 70 g of pentamethylcyclopentadienyl lithium with the yield of 86%;
step 2: 22 g (0.081mol) of molybdenum pentachloride, 60 ml of toluene and 250 ml of tetrahydrofuran are sequentially added into a 500 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a first solution. 38 g (0.084mol) of the pentaphenylcyclopentadienyl lithium prepared in the step 1, 8 g (0.211mol) of sodium borohydride and 500 ml of tetrahydrofuran are sequentially added into a 2000 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a second solution. At the temperature of minus 10 ℃, dropwise adding the first solution into the second solution, recovering to room temperature after dropwise adding, stirring at room temperature for 3 hours, heating to 65 ℃, heating for 24 hours, carrying out vacuum drying on the solvent, adding 1000 ml of n-hexane for extraction, passing through diatomite, concentrating the filtrate to 500 ml, adding 30 ml (0.372mol) of chloroform, stirring at room temperature for 10 hours, filtering, washing the solid with n-hexane, and carrying out vacuum drying to obtain 67 g of bis (pentaphenylcyclopentadienyl) molybdenum dichloride with the yield of 79%;
and step 3: to a 500 ml Schlenk flask were added 50 g (0.047mol) of bis (pentaphenylcyclopentadienyl) molybdenum dichloride prepared in step 2 and 300 ml of methyl t-butyl ether in this order, and then cooled to 0 ℃ and, after slowly adding 6.4 g (0.098mol) of lithium methylethylamine with stirring, stirred at room temperature for 10 hours. Then, the solvent is pumped out under reduced pressure, n-hexane is added for extraction, diatomite is filtered, the solvent n-hexane is pumped out from the filtrate, and 41 g of bis (methylethylamino) bis (pentaphenylcyclopentadienyl) molybdenum product is obtained, wherein the yield is 80%.
The bis (methylethylamino) bis (pentaphenylcyclopentadienyl) molybdenum prepared in the example is subjected to element analysis and detection, and the theoretical value is as follows: 82.7C, 6.0H, 2.5N, 8.7 Mo, measurement: 83.1 percent of C, 6.2 percent of H, 2.9 percent of N and 8.1 percent of Mo.
Example 7
This example provides a diamido-dimocene-molybdenum complex and a preparation method thereof, which are substantially the same as the method in example 1, except that the molar ratio of molybdenum pentachloride to chloroform is different, and the specific steps are as follows:
step 1: 50 g (0.367mol) of pentamethylcyclopentadiene and 50 ml of n-hexane were added to a 500 ml Schlenk bottle under an argon atmosphere to lower the temperature of the system to 0 ℃ and 147 ml of an n-hexane solution of n-butyllithium was added dropwise thereto at a concentration of 2.5 mol/l. After the dropwise addition, the room temperature is recovered and the reaction is carried out for 2 hours, the filtration is carried out, the normal hexane is used for washing and drying, 41 g of pentamethylcyclopentadienyl lithium is obtained, and the yield is 80%;
step 2: 10 g (0.037mol) of molybdenum pentachloride, 25 ml of toluene and 125 ml of tetrahydrofuran are sequentially added into a 250 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a first solution. 11 g (0.077mol) of pentamethylcyclopentadienyl lithium prepared in the step 1, 4 g (0.106mol) of sodium borohydride and 375 ml of tetrahydrofuran are sequentially added into a 500 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a second solution. At the temperature of minus 10 ℃, dropwise adding the first solution into the second solution, recovering to room temperature after dropwise adding, stirring at room temperature for 3 hours, heating to 65 ℃, heating for reaction for 24 hours, pumping out the solvent under reduced pressure, adding 400 ml of n-hexane for extraction, passing through diatomite, concentrating the filtrate to 250 ml, adding 9 ml (0.111mol) of chloroform, stirring at room temperature for 10 hours, filtering, washing the solid with n-hexane, and drying in vacuum to obtain 34 g of bis (pentamethylcyclopentadienyl) molybdenum dichloride with the yield of 81%;
and step 3: 40 g (0.092mol) of bis (pentamethylcyclopentadienyl) molybdenum dichloride prepared in step 2 and 300 ml of methyl tert-butyl ether were sequentially added to a 500 ml Schlenk flask, cooled to 0 ℃ and stirred at room temperature for 10 hours after 9 g (0.176mol) of lithium dimethylamine was slowly added with stirring. Then, the solvent is pumped out under reduced pressure, n-hexane is added for extraction, diatomite is added, the solvent n-hexane is pumped out from the filtrate, and 33 g of bis (dimethylamino) bis (pentamethylcyclopentadienyl) molybdenum product is obtained, wherein the yield is 80%.
The element analysis and detection of the bis (dimethylamino) bis (pentamethylcyclopentadienyl) molybdenum prepared in the example have the following theoretical values: C63.4H: 9.3, N6.2, Mo 21.1, found: 62.6 percent of C, 9.6 percent of H, 6.8 percent of N and 21.3 percent of Mo.
Example 8
This example provides a diamino molybdenum metallocene complex and a preparation method thereof, which is substantially the same as the method in example 1, except that the temperatures of the first cooling and the second cooling are different, and the specific steps are as follows:
step 1: 50 g (0.367mol) of pentamethylcyclopentadiene and 50 ml of n-hexane were added to a 500 ml Schlenk bottle under an argon atmosphere to lower the temperature of the system to 0 ℃ and 147 ml of an n-hexane solution of n-butyllithium was added dropwise thereto at a concentration of 2.5 mol/l. After the dropwise addition, the room temperature is recovered and the reaction is carried out for 2 hours, the filtration is carried out, the normal hexane is used for washing and drying, 41 g of pentamethylcyclopentadienyl lithium is obtained, and the yield is 80%;
step 2: 10 g (0.037mol) of molybdenum pentachloride, 25 ml of toluene and 125 ml of tetrahydrofuran are sequentially added into a 250 ml Schlenk bottle, stirred and dissolved, and then cooled to 0 ℃ to obtain a first solution. 11 g (0.077mol) of pentamethylcyclopentadienyl lithium prepared in the step 1, 4 g (0.106mol) of sodium borohydride and 375 ml of tetrahydrofuran are sequentially added into a 500 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a second solution. At the temperature of minus 10 ℃, dropwise adding the first solution into the second solution, recovering to room temperature after dropwise adding, stirring at room temperature for 3 hours, heating to 65 ℃, heating for reaction for 24 hours, pumping out the solvent under reduced pressure, adding 400 ml of n-hexane for extraction, passing through diatomite, concentrating the filtrate to 250 ml, adding 13 ml (0.161mol) of chloroform, stirring at room temperature for 10 hours, filtering, washing the solid with n-hexane, and drying in vacuum to obtain 12 g of bis (pentamethylcyclopentadienyl) molybdenum dichloride with the yield of 77%;
and step 3: 40 g (0.092mol) of bis (pentamethylcyclopentadienyl) molybdenum dichloride prepared in step 2 and 300 ml of methyl tert-butyl ether were sequentially added to a 500 ml Schlenk flask, cooled to 0 ℃ and stirred at room temperature for 10 hours after 9 g (0.176mol) of lithium dimethylamine was slowly added with stirring. Then, the solvent is pumped out under reduced pressure, n-hexane is added for extraction, diatomite is added, the solvent n-hexane is pumped out from the filtrate, and 33 g of bis (dimethylamino) bis (pentamethylcyclopentadienyl) molybdenum product is obtained, wherein the yield is 80%.
The element analysis and detection of the bis (dimethylamino) bis (pentamethylcyclopentadienyl) molybdenum prepared in the example have the following theoretical values: C63.4H: 9.3, N6.2, Mo 21.1, found: 62.6 percent of C, 9.6 percent of H, 6.8 percent of N and 21.3 percent of Mo.
Comparative example 1
The comparative example provides a diamino molybdenum metallocene complex and a preparation method thereof, which are basically the same as the method of example 1, and are different only in that chloroform is replaced by dichloromethane with the same amount, and the specific steps are as follows:
step 1: 50 g (0.367mol) of pentamethylcyclopentadiene and 50 ml of n-hexane were added to a 500 ml Schlenk bottle under an argon atmosphere to lower the temperature of the system to 0 ℃ and 147 ml of an n-hexane solution of n-butyllithium was added dropwise thereto at a concentration of 2.5 mol/l. After the dropwise addition, the room temperature is recovered and the reaction is carried out for 2 hours, the filtration is carried out, the normal hexane is used for washing and drying, 41 g of pentamethylcyclopentadienyl lithium is obtained, and the yield is 80%;
step 2: 10 g (0.037mol) of molybdenum pentachloride, 25 ml of toluene and 125 ml of tetrahydrofuran are sequentially added into a 250 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a first solution. 11 g (0.077mol) of pentamethylcyclopentadienyl lithium prepared in the step 1, 4 g (0.106mol) of sodium borohydride and 375 ml of tetrahydrofuran are sequentially added into a 500 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a second solution. At the temperature of minus 10 ℃, dropwise adding the first solution into the second solution, recovering to room temperature after dropwise adding, stirring at room temperature for 3 hours, heating to 65 ℃, heating for reaction for 24 hours, pumping out the solvent under reduced pressure, adding 400 ml of n-hexane for extraction, passing through diatomite, concentrating the filtrate to 250 ml, adding 10 ml (0.161mol) of dichloromethane, stirring at room temperature for 10 hours, filtering, washing the solid with n-hexane, and drying in vacuum to obtain 6 g of bis (pentamethylcyclopentadienyl) molybdenum dichloride with the yield of 38%;
and step 3: 40 g (0.092mol) of bis (pentamethylcyclopentadienyl) molybdenum dichloride prepared in step 2 and 300 ml of methyl tert-butyl ether were sequentially added to a 500 ml Schlenk flask, cooled to 0 ℃ and stirred at room temperature for 10 hours after 9 g (0.176mol) of lithium dimethylamine was slowly added with stirring. Then, the solvent is pumped out under reduced pressure, n-hexane is added for extraction, diatomite is added, the solvent n-hexane is pumped out from the filtrate, and 33 g of bis (dimethylamino) bis (pentamethylcyclopentadienyl) molybdenum product is obtained, wherein the yield is 80%.
The element analysis and detection are carried out on the bis (dimethylamino) bis (pentamethylcyclopentadienyl) molybdenum prepared by the comparative example, and the theoretical value is as follows: C63.4H: 9.3, N6.2, Mo 21.1, found: 62.4 percent of C, 9.7 percent of H, 6.6 percent of N and 20.8 percent of Mo.
Comparative example 2
The comparative example provides a diamino molybdenum dicyclopentadienyl complex and a preparation method thereof, which are basically the same as the method of the example 1, and are different only in that chloroform is replaced by carbon tetrachloride, and the specific steps are as follows:
step 1: 50 g (0.367mol) of pentamethylcyclopentadiene and 50 ml of n-hexane were added to a 500 ml Schlenk bottle under an argon atmosphere to lower the temperature of the system to 0 ℃ and 147 ml of an n-hexane solution of n-butyllithium was added dropwise thereto at a concentration of 2.5 mol/l. After the dropwise addition, the room temperature is recovered and the reaction is carried out for 2 hours, the filtration is carried out, the normal hexane is used for washing and drying, 41 g of pentamethylcyclopentadienyl lithium is obtained, and the yield is 80%;
step 2: 10 g (0.037mol) of molybdenum pentachloride, 25 ml of toluene and 125 ml of tetrahydrofuran are sequentially added into a 250 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a first solution. 11 g (0.077mol) of pentamethylcyclopentadienyl lithium prepared in the step 1, 4 g (0.106mol) of sodium borohydride and 375 ml of tetrahydrofuran are sequentially added into a 500 ml Schlenk bottle, stirred and dissolved, and then cooled to-10 ℃ to obtain a second solution. At the temperature of minus 10 ℃, dropwise adding the first solution into the second solution, recovering to room temperature after dropwise adding, stirring at room temperature for 3 hours, heating to 65 ℃, heating for 24 hours, performing reaction under reduced pressure, draining the solvent, adding 400 ml of n-hexane for extraction, passing through diatomite, concentrating the filtrate to 250 ml, adding 16 ml (0.161mol) of carbon tetrachloride, stirring at room temperature for 10 hours, filtering, washing the solid with n-hexane, and performing vacuum drying to obtain 2 g of bis (pentamethylcyclopentadienyl) molybdenum dichloride with the yield of 13%;
and step 3: 40 g (0.092mol) of bis (pentamethylcyclopentadienyl) molybdenum dichloride prepared in step 2 and 300 ml of methyl tert-butyl ether were sequentially added to a 500 ml Schlenk flask, cooled to 0 ℃ and stirred at room temperature for 10 hours after 9 g (0.176mol) of lithium dimethylamine was slowly added with stirring. Then, the solvent is pumped out under reduced pressure, n-hexane is added for extraction, diatomite is added, the solvent n-hexane is pumped out from the filtrate, and 33 g of bis (dimethylamino) bis (pentamethylcyclopentadienyl) molybdenum product is obtained, wherein the yield is 80%.
The element analysis and detection are carried out on the bis (dimethylamino) bis (pentamethylcyclopentadienyl) molybdenum prepared by the comparative example, and the theoretical value is as follows: C63.4H: 9.3, N6.2, Mo 21.1, found: 62.8 percent of C, 9.1 percent of H, 6.6 percent of N and 21.3 percent of Mo.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
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.
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| US11390638B1 (en) | 2021-01-12 | 2022-07-19 | Applied Materials, Inc. | Molybdenum(VI) precursors for deposition of molybdenum films |
| US11434254B2 (en) | 2021-01-12 | 2022-09-06 | Applied Materials, Inc. | Dinuclear molybdenum precursors for deposition of molybdenum-containing films |
| US11459347B2 (en) | 2021-01-12 | 2022-10-04 | Applied Materials, Inc. | Molybdenum(IV) and molybdenum(III) precursors for deposition of molybdenum films |
| US11760768B2 (en) | 2021-04-21 | 2023-09-19 | Applied Materials, Inc. | Molybdenum(0) precursors for deposition of molybdenum films |
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| US11390638B1 (en) | 2021-01-12 | 2022-07-19 | Applied Materials, Inc. | Molybdenum(VI) precursors for deposition of molybdenum films |
| US11434254B2 (en) | 2021-01-12 | 2022-09-06 | Applied Materials, Inc. | Dinuclear molybdenum precursors for deposition of molybdenum-containing films |
| US11459347B2 (en) | 2021-01-12 | 2022-10-04 | Applied Materials, Inc. | Molybdenum(IV) and molybdenum(III) precursors for deposition of molybdenum films |
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