- The Synthesis and Properties of Dimethylgallane: Structure of the Dimer Me2Ga(μ-H)2GaMe2 in the Gas Phase as determined by Electron Diffraction
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Dimethylgallane, best synthesised by the reaction between trimethylgallane and sodium tetrahydrogallate, has been characterised by its spectroscopic and chemical properties; electron diffraction has established the structure of the dimer Me2Ga(μ-H)2GaMe2,
- Baxter, Paul L.,Downs, Anthony J.,Goode, Michael J.,Rankin, David W. H.,Robertson, Heather E.
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- "Metastable" Lu(GaMe4)3 reacts like masked [LuMe3]: Synthesis of an unsolvated lanthanide dimethyl complex
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Homoleptic tetramethylgallate Lu(GaMe4)3 reacts selectively with superbulky (TptBu,Me)H according to a methane elimination reaction, affording the quantitative formation of monomeric base-free low-coordinate (Tp
- Zimmermann, Melanie,Litlabo, Rannveig,Toernroos, Karl W.,Anwander, Reiner
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- Coordination complexes derived from 3,6-di(2-pyridyl)-1,4-dihydro-1,2,4,5-tetrazine (DPDHT). Synthesis and molecular structure of [(DPT)(GaMe2)2]
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The facile reaction of 3,6-di(2-pyridyl)-1,4-dihydro-1,2,4,5-tetrazine (DPDHT) (1) with trimethylgallium has resulted in the formation of the purple crystalline product, [(DPT)(GaMe2)2] (2), via methane elimination. Crystals of [(DPT)(GaMe2)2] are orthorhombic, Pbca, a = 15.380(2), b = 21.642(4), c = 11.355(2) A, Z = 8. The structure was solved by heavy-atom Patterson methods and refined by full-matrix least-squares procedures to R = 0.035 for 1570 reflections with I ≥ 3σ(I) (Rw = 0.063 for all 4342 reflections). The [(DPT)(GaMe2)2] molecule is roughly planar (apart from the four methyl groups), in contrast to the folded structure of the DPDHT molecule; molecular dimensions are normal.
- Preston, Peter N.,Rettig, Steven J.,Storr, Alan,Trotter, James
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- Aryl-NHC-group 13 trimethyl complexes: structural, stability and bonding insights
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Treatment of aromatic N-substituted N-heterocyclic carbenes (NHCs) with trimethyl-gallium and -indium yielded the new Lewis acid-base adducts, IMes·GaMe3 (1), SIMes·GaMe3 (2), IPr·GaMe3 (3), SIPr·GaMe3 (4), IMes·InMe3 (5), SIMes·InMe3 (6), IPr·InMe3 (7), and SIPr·InMe3 (8), with all complexes being identified by X-ray diffraction, IR, and multinuclear NMR analyses. Complex stability was found to be largely dependent on the nature of the constituent NHC ligands. Percent buried volume (%VBur) and topographic steric map analyses were employed to quantify and elucidate the observed trends. Additionally, a detailed bond snapping energy (BSE) decomposition analysis focusing on both steric and orbital interactions of the M-NHC bond (M = Al, Ga and In) has been performed.
- Wu, Melissa M.,Gill, Arran M.,Yunpeng, Lu,Yongxin, Li,Ganguly, Rakesh,Falivene, Laura,García, Felipe
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- Homoleptic and heteroleptic gallium(III) compounds containing monosubstituted cyclopentadienyl ligands: Ga(C5H4Me)3, Ga(C5H4SiMe3)3, and R2Ga(C5H4
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The new gallium(III) cyclopentadienyl derivatives Ga(C5H4Me)3 and Ga(C5SiMe3)3 have been synthesized by metathetical reactions. Subsequent stoichiometric ligand redistribution reactions wit
- Beachley Jr.,Mosscrop, Michael T.
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- Reactivity of carbonyl-functionalized phosphaalkenes RC(O)P=C(NMe2)2 (R = tBu, ph) towards electrophiles
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The reaction of the carbonyl-functionalized phosphaalkenes RC(O)P=C(NMe2)2 [R = tBu (2a), Ph (2b)] with protic acids and alkylating reagents occurred at the two-coordinate phosphorus atom to give the phosphanyl-substituted carbocations 3a,b and 4a,b. In contrast, treatment with Me3SiOSO2CF3 resulted in attack at the oxygen atom by the silyl group, and the formation of [RC(OSiMe3)= PC(NMe2)2]SO3CF3 (5a,b). Similarly, the Lewis acids B(C6F5)3, Al(tBu)2Cl and AlMe3 were ligated to the oxygen atom of the carbonyl group. Two equivalents of GaMe3 were added to the oxygen and phosphorus atom of the phosphaalkene to yield the thermolabile complexes [RC(OGaMe3)=P(GaMe3)C(NMe2)2] (10a,b). In contrast, one molecule of InMe3 was bound to the phosphorus center of the phosphorus compound. Reaction of the phosphaalkenes with [Ni(CO)4], [Fe2(CO)9] or [{(Z)-cyclooctene}Cr(CO)5] also took place at the pnictogen atom, resulting in complexes of the type [RC(O)P{M(CO)(n)}C(NMe2)2] (R = tBu, Ph; M = Ni, n = 3; Fe, n = 4; Cr, n = 5). The chemical transformations reported here underline the versatile chemistry of phosphaalkenes and emphasize a relationship between carbonyl- functionalized phosphaalkenes and the well-investigated class of phosphorus ylides. X-ray structures of compounds 6b, 7b*, 10a, 11a and 12a are reported.
- Weber, Lothar,Uthmann, Stefan,Stammler, Hans-Georg,Neumann, Beate,Schoeller, Wolfgang W.,Boese, Roland,Bl?ser, Dieter
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- A new synthetic route to trimethylgallium
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A new synthetic route to trimethylgallium was developed. It is based on preparation of gallium methyl derivatives by the Green reaction, followed by their alkylation with methyl Grignard reagent. The suggested procedure is well reproducible, with the yield of pure trimethylgallium exceeding 90%.
- Revin,Artemov,Sazonova
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- Polymorphism in the crystal structures of the group 13 trimethyls
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Crystal structure have been determined for trimethylboron, BMe3, and for a new polymorph of trimethylgallium, GaMe3; in addition, the crystal structure of trimethylthallium, TlMe3, has been redetermined. The BMe3 crystal structure represents a new structural type for the group 13 trimethyl derivatives in the solid state. In contrast to its heavier analogues, it consists of layer containing only very weakly interacting BMe3 molecules. GaMe3 forms a ladder-like pseudo-polymer via long gallium-to-methyl intermolecular interactions with Ga...C distances in the range 3.096(3)-3.226(4) A. This is compared with a recently reported crystal structure of a polymorph, which, like InMe3 and TlMe3, is characterized by the formation of pseudo-tetramers. The effects of crystallization and secondary interactions have been analyzed by comparison with related crystallographic, gas-phase electron diffraction, and spectroscopic studies of these and other trimethyl derivatives of the group 13 elements. The energetic differences between polymorphs of BMe3, GaMe3, and InMe3 have been explored by plane wave DFT calculations. The energy differences between the BMe3-like layered structure and the InMe3-like pseudo-tetrameric structure are calculated to be -1.7, +3.6, and +10.4 kJ mol-1 for BMe3, GaMe3, and InMe3, respectively.
- Boese, Roland,Downs, Anthony J.,Greene, Timothy M.,Hall, Alexander W.,Morrison, Carole A.,Parsons, Simon
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- 71Ga NMR studies of mixtures of gallium trichloride and trimethylgallium
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71Ga NMR spectra of solutions of GaCl3 and Me3Ga, and of binary mixtures of GaCl3-Me3Ga, in n-heptane have been recorded.The resonance signals for both Me3Ga and GaCl3 are unchanged on dilution over the temperature range 20-100 deg C.Mixtures of GaCl3 and Me3Ga show only one resonance signal, whose chemical shift is determined predominantly by the nature of the coordination at gallium, indicating rapid chemical exchange of the species involved.The results of studies of methanolysis and hydrolysis, and of adduct formation, are also discussed.The 71Ga resonances of several possible external standards in the temperature range 20-100 deg C are also reported.The 71Ga NMR signal of a solution of GaCl4- in 6 M aqueous hydrochloric acid, for which δ(71Ga) = 250 +/- 0.5 ppm downfield from the signal of a 1 M solution of 3+3- in 1 M HClO4, is recommended as a temperature-independent external standard for gallium NMR studies.
- Cerny, Z.,Machacek, J.,Fusek, J.,Kriz, O.,Casensky, B.,Tuck, Dennis G.
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- Process for preparing alkyl metal compounds
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The invention relates to a method for producing alkyl metal compounds, starting materials for the production of trialkyl gallium and trialkyl indium comprise metallic indium or metallic gallium, at least one alkyl donor, a reducing agent and a solvent; the alkyl donor is alkyl halide; R in MR 2-4 represents alkyl group, 2 to 4 R groups are independently selected from the same or different alkyl groups; M is especially aluminum, gallium or indium; high purity gallium or indium or aluminum is used; sesquialkyl aluminum chloride is used as a reaction promoter, and the metal gallium or metal indium is reacted with alkyl chloride of the alkyl donor at low temperature and low pressure to generate sesquialkyl gallium chloride or sesquialkyl indium chloride; when the sesquialkyl gallium chloride or indium sesquialkyl chloride is reduced to the trialkyl gallium or trialkyl indium by a reducing agent, metal gallium or metal indium is necessarily generated simultaneously; the newly generated metal gallium or metal indium reacts with chloromethane (ethyl) in situ, so that the starting materials are fully utilized. The yield of the two steps is almost complete. The new synthetic route is an environment-friendly green process.
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Paragraph 0122-0125
(2020/05/30)
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- METHOD FOR STORING AND/OR TRANSPORTING GALLIUM CHLORIDE
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Method for storing and/or transporting GaCl3 involving the step of adding an aluminium compounds of the formula R3-xAlClx, wherein R is a linear or branched alkyl group with 1-8 carbon atoms and x is 0 or 1, to said GaCl3 in an Al/Ga molar ratio of at least 0.2, thereby forming a liquid formulation, followed by introducing said liquid formulation in a container.
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(2019/05/22)
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- PROCESS FOR PURIFICATION OF DIMETHYL ALUMINIUM CHLORIDE
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Process for the removal of gallium compounds from dimethyl aluminium chloride (DMAC)-containing compositions, comprising the steps of: (i) adding methyl aluminium sesquichloride (MASC) to said DMAC-containing composition, thereby forming dimethyl aluminium chloride (DMAC) and methyl gallium chloride (MexGaCI(3-X), wherein x=1 or 2), (ii) reducing said methyl gallium chloride with metallic aluminium to form methyl aluminium dichloride (MADC) and metallic gallium, and (iii) removing metallic gallium from the DMAC-containing composition.
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(2019/07/19)
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- PROCESS FOR THE PREPARATION OF TRIMETHYL METAL COMPOUNDS
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Process for the preparation of a trimethyl metal compound with the formula M(CH3)3, said process comprising the step of reacting a trialkyl metal compound of the formula M(R)3 with trimethyl aluminium [AI(CH3)3] to form said trimethyl metal compound with the formula M(CH3)3, wherein M is selected from the group consisting of Ga and In, and R is a linear or branched alkyl group with 2 to 8 carbon atoms.
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Page/Page column 7-8
(2017/03/21)
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- Method for producing trialkylgallium
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PROBLEM TO BE SOLVED: To provide a method for producing trialkylgallium by a convenient method and without complex aftertreatment. SOLUTION: The present invention relates to a method for producing trialkylgallium represented by formula (4) by the reaction of trialkyl aluminum to trihalogeno gallium in the presence of at least one of an amine compound represented by formula (3) and a quaternary onium salt (R1 is a C7-12 linear or branched alkyl group) (R is a C1-6 alkyl group). SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0079; 0080
(2017/02/24)
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- Method for producing trialkylgallium
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PROBLEM TO BE SOLVED: To provide a method for producing trialkylgallium by a simple method using an ether compound. SOLUTION: The method for producing a trialkylgallium is provided in which, when a trialkylaluminum and a trihalogenogallium are reacted in the presence of an ether compound represented by a formula (3) and then the trialkylgallium is obtained from the resultant reaction liquid by distillation, at least one compound is caused to be present which is selected from inorganic salts such as alkali metal halides or alkaline earth metal halides, or tertiary amines such as trialkylamines, N-alkylpiperidines, and N-alkylindoles. (R1 is a C1-6 linear or branched alkyl group; R2 is a C3-8 linear or branched alkyl group; and, further, R1 and R2 may be bonded to each other to form a ring.) SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0040-0043
(2017/02/28)
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- The continuous reaction device and method of using the continuous composite (by machine translation)
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PROBLEM TO BE SOLVED: compounds with high productivity can be generated. SOLUTION: 1 the raw material supply section 12 and a first, a second and 2 the raw material supply section 14, and a reaction part 18, the first reaction part 1 from the raw material supply section 1 and a second quantity of raw material, the raw material supply section 2 from the first reaction part 2 and a second quantity of raw material, the raw material supply section 1 from the first reaction part 1 and a second temperature of the raw material, the raw material supply section 2 from the first reaction part 2 and supplied to the temperature of the raw material, and having a control part 22, a continuous reaction device as shown in the drawing. Selected drawing: fig. 1 (by machine translation)
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Paragraph 0187
(2017/01/02)
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- Reaction of a germylene, stannylene, or plumbylene with trimethylaluminum and trimethylgallium: Insertion into Al-C or Ga-C bonds, a reversible metal-carbon insertion equilibrium, and a new route to diplumbenes
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The reaction of the tetrylenes Ge(ArMe6)2, Sn(ArMe6)2, and Pb(ArMe6)2 [ArMe6 = C6H3-2,6-(C6H2-2,4,6-(CH3)3)2] with the group 13 metal alkyls trimethylaluminum and trimethylgallium afforded (ArMe6)2Ge(Me)AlMe2 (1), (ArMe6)2Ge(Me)GaMe2 (2), and (ArMe6)2Sn(Me)GaMe2 (3) in good yields via insertion reaction routes. In contrast, the reaction of AlMe3 with Sn(ArMe6)2 afforded the [1.1.1]propellane analogue Sn2{Sn(Me)ArMe6}3 (5) in low yield, and the reaction of AlMe3 or GaMe3 with Pb(ArMe6)2 resulted in the formation of the diplumbene {Pb(Me)ArMe6}2 (6) and AlArMe6Me2 (7) or GaArMe6Me2 (8) via metathesis. The reaction of Sn(ArMe6)2 with gallium trialkyls was found to be reversible under ambient conditions and analyzed through the reaction of Sn(ArMe6)2 with GaEt3 to form (ArMe6)2Sn(Et)GaEt2 (4), which displayed a dissociation constant Kdiss and ΔGdiss of 8.09(6) × 10-3 and 11.8(9) kJ mol-1 at 296 °C. The new compounds were characterized by X-ray crystallography, NMR (1H, 13C, 119Sn, and 207Pb), IR, and UV-vis spectroscopies.
- Erickson, Jeremy D.,Fettinger, James C.,Power, Philip P.
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p. 1940 - 1948
(2015/06/16)
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- High-purity trialkylgallium and its manufacturing method (by machine translation)
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PROBLEM TO BE SOLVED: To provide a high purity trialkyl gallium and a simple manufacturing method of the compound.SOLUTION: There is a method of obtaining trialkyl gallium represented by the formula (3) as a main distillate by mixing and reacting trialkyl aluminum represented by the formula (1) and trihalogeno gallium represented by the formula (2), removing a first drop with a reflux ratio of 10 to 25 and setting the reflux ratio at 6 to 15. In the formula (1), R represents an alkyl group having 1 to 6 carbon atoms. In the formula (2), X represents a halogen atom.
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Paragraph 0023-0024
(2021/04/27)
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- Process for trimethylgallium with high yield
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The present invention relates to a method to manufacture trimethylgallium at high yields and, more specifically, to a method to manufacture trimethylgallium at high yields from gallium in a powder state, and methyl groups in a liquid state using a magnesium catalyst. The present invention provides a method to manufacture trimethylgallium comprising the steps of: stirring magnesium powder under an argon atmosphere; mixing the magnesium powder with gallium powder; forming a first solution by mixing the mixture of the magnesium powder and the gallium powder with ether as a solvent; forming a second solution by adding drops of methyl iodide to the first solution; forming a third solution by mixing the second solution with the ether and mesitylene; raising the temperature of the third solution; and obtaining trimethylgallium by leaving the third solution of which the temperature has been raised at room temperature.
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Paragraph 0038-0042
(2016/12/16)
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- PRODUCTION OF TRI-ALKYL COMPOUNDS OF GROUP 3A METALS
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Disclosed herein are methods of making compounds of the formula: (R)3M, where M is gallium, indium or thallium; and each R is independently C1-C10 alkyl; the methods comprising: combining the metal, M, the trihalide of the metal, MX3, where X is I, Br or Cl; and a halomethane to form (R)3M2X3; treating the (R)3M2X3 with a reducing agent in a solvent to form (R)3M.
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Paragraph 0046
(2014/07/07)
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- PROCESS FOR PREPARING TRIALKYLGALLIUM COMPOUNDS
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The invention relates to a process for preparing trialkylgallium compounds of the general formula R3Ga. The process is based on the reaction of gallium trichloride (GaCh), optionally in a mixture with partially alkylated products, with an alkylaluminium compound of the type RaAlClb (where R═C1-C5-alkyl, a=1, 2 or 3, b=0, 1 or 2 and a+b=3) in the presence of at least two alkali metal halides (e.g. NaCl and KCl) as auxiliary base. Preference is given to using alkylaluminium sesquichloride (R3Al2Cl3) or trialkylaluminium (R3Al). The reaction mixture is heated to a temperature in the range from 120° C. to 250° C. and the trialkylgallium compound formed is separated off via a separator which is operated at a temperature which is more than 30° C. below the boiling point of the most volatile partially alkylated product. Complete alkylation is achieved here and partially alkylated products are recirculated to the reaction mixture. In a further step, the reaction mixture can be heated to a maximum of 350° C. and the remaining fully alkylated and partially alkylated products can be separated off. The process provides a high yield of trialkylgallium compound and displays high gallium utilization; the products are used, e.g., as precursors for MOCVD processes.
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Paragraph 0114-0116
(2014/09/29)
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- METHODS OF PRODUCING TRIMETHYLGALLIUM
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Methods of preparing compounds of the formula: Me3M, wherein M is gallium, indium or thallium; the methods comprising reacting at least three equivalents of a halomethane compound with a compound of the formula (R)3M; wherein each R is independently C2-C8 alkyl.
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Page/Page column 8
(2014/06/11)
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- ORGANOMETALLIC COMPOUND PREPARATION
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A method of continuously manufacturing an organometallic compound is provided where two or more reactants are conveyed to a contacting zone of a reactor in a manner so as to maintain a laminar flow of the reactants; and causing the reactants to form the organometallic compound.
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Paragraph 0044
(2013/08/28)
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- ORGANOMETALLIC COMPOUND PREPARATION
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A method of continuously manufacturing organometallic compounds is provided where two or more reactants are conveyed to a reactor having a laminar flow contacting zone, a heat transfer zone, and a mixing zone having a turbulence-promoting device; and causing the reactants to form the organometallic compound.
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Paragraph 0054
(2013/08/28)
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- Preparation of Tri-Alkyl Gallium or Tri-Alkyl Indium Compounds
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Trialkyl metal compounds, such as trialkyl gallium and indium compounds, are prepared in high yield and high purity by the addition of a trialkyl aluminum compound to a mixture prepared by adding a metal trihalide, e.g., GaCl3 or InCl3, and a halide salt of a monovalent metal to an ionic liquid such as a molten salt of the formula M[AlRn X(4-n)] wherein M is a monovalent metal such as Li, Na, K or Cs, R is an alkyl group X is a halide and n is a number from 1 to 3, typically at temperatures of from 75 to 160° C.
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Paragraph 0060
(2013/08/14)
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- PROCESS FOR PREPARING TRIALKYLGALLIUM COMPOUNDS
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The invention relates to a process for preparing trialkylgallium compounds of the general formula R3Ga. The process is based on the reaction of gallium trichloride (GaCh), optionally in a mixture with partially alkylated products, with an alkylaluminium compound of the type RaAICIb (where R = C1-C5-alkyl, a = 1, 2 or 3, b = 0, 1 or 2 and a + b = 3) in the presence of at least two alkali metal halides (e.g. NaCI and KCI) as auxiliary base. Preference is given to using alkylaluminium sesquichloride (R3AI2CI3) or trialkylaluminium (R3AI). The reaction mixture is heated to a temperature in the range from 120°C to 250°C and the trialkylgallium compound formed is separated off via a separator which is operated at a temperature which is more than 30°C below the boiling point of the most volatile partially alkylated product. Complete alkylation is achieved here and partially alkylated products are recirculated to the reaction mixture. In a further step, the reaction mixture can be heated to a maximum of 350°C and the remaining fully alkylated and partially alkylated products can be separated off. The process provides a high yield of trialkylgallium compound and displays high gallium utilization; the products are used, e.g., as precursors for MOCVD processes.
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Page/Page column 22
(2013/06/27)
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- PROCESS FOR PREPARING TRIALKYL COMPOUNDS OF METALS OF GROUP IIIA
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The invention relates to a process for preparing trialkylmetal compounds of the general formula R3M (where M = metal of group llIA of the Periodic Table of the Elements (PTE), preferably gallium or indium, and R = C1-C5-alkyl, preferably methyl or ethyl). The process is based on the reaction of metal trichloride (MeCl3) with alkylaluminium sesquichloride (R3AI2CI3) in the presence of at least one alkali metal halide as auxiliary base. The reaction mixture is heated to a temperature above 120°C and the trialkylmetal compound is separated off from the reaction mixture via a separator, with partially alkylated products being at the same time recirculated to the reaction mixture. In a further step, the reaction mixture is heated to a maximum of 350°C and the remaining alkylated and partially alkylated products are separated off. The products obtained in this way can optionally be recycled in the process. The process displays a high yield of trialkylmetal compound and also a high metal utilization; the products are used as precursors for MOCVD processes.
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Page/Page column 15-16
(2013/06/27)
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- Organometallic compound preparation
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A method of continuously manufacturing an organometallic compound is provided where two or more reactants are conveyed to a contacting zone of a reactor in a manner so as to maintain a laminar flow of the reactants; and causing the reactants to form the organometallic compound.
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Paragraph 0043
(2013/03/26)
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- The synthesis and deep purification of GaEt3. Reversible complexation of adducts MAlk3 (M = Al, Ga, In; Alk = Me, Et) with phenylphosphines
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Optimal parameters of organomagnesium technique of synthesis of triethylgallium have been defined. Various techniques of deep purification of triethylgallium to the extent required in metalorganic vapor-phase epitaxy MOVPE have been studied: by way of residue ether displacement through high-performance rectification and interaction with high pure aluminum and gallium trichloride, and by way of reversible complexation with triphenylphosphine, 1,3-bis(diphenylphosphine)propane and 1,5- bis(diphenylphosphine)pentane. Advantages and disadvantages of each technique have been identified. We have shown high performance of adduct purification technique covering trimethyl and triethyl derivatives of aluminum, gallium and indium. The structure of donor-acceptor complexes between metal alkyls and the above-mentioned phosphines have been verified using H and 31P NMR spectroscopy and X-ray studies, as well as quantum chemical calculations. Thermal stability of triethylgallium and oxidation of its adducts with phosphines have been studied.
- Shatunov,Korlyukov,Lebedev,Sheludyakov,Kozyrkin,Orlov, V.Yu.
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p. 2238 - 2251
(2011/06/22)
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- Bis-and tris(dimethylgallyl)benzenes: Synthesis, solid-state structures, and redistribution reactions
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derivatives containing dimethylgallyl substituents in 1,3- (compounds 5 and 6), 1,4- (compound 9), and 1,3,5-position (compound 12) were prepared by reaction of the corresponding chloromercuri- obenzenes with an excess of trimethylgallium at higher temperatures. These compounds decompose in solution at room temperature and in the solid state upon mild heating with elimination of trimethylgallium to give oligomeric condensation products of unknown detailed composition. These condensation products can be transformed back into the starting compounds by treatment with an excess of trimethylgallium at higher temperatures. Highly air-sensitive crystals of 5, 6, 9, and 12 suitable for an X-ray analysis are obtained from trimethylgallium as solvent. The X-ray crystallographic studies revealed the presence of higher coordinate gallium atoms, which lead to the formation of strand- or sheet-like polymers. A trigonal- bipyramidal coordination sphere is observed for the gallium atoms in 9. A distorted tetrahedral coordination is found for the gallium atoms in 5, 6, and 12. The latter compounds possess asymmetric aryl-dimethylgallyl bridging units.
- Jutzi, Peter,Izundu, Joseph,Sielemann, Henning,Neumann, Beate,Stammler, Hans-Georg
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p. 2619 - 2624
(2009/09/30)
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- Aryl(dimethyl)gallium compounds and methyl(diphenyl)gallium: Synthesis, structure, and redistribution reactions
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Treatment of diphenylmercury with an excess of trimethylgallium at higher temperatures resulted in the formation of dimethyl(phenyl)gallium (1). Similarly, reaction of 1-chloromercurio(4-methylbenzene) and 1-chloromercurio(4-tert-butylbenzene) with an excess of trimethylgallium gave dimethyl(4methylphenyl)gallium (2) and dimethyl(4-tert-butylphenyl)gallium (3), respectively. Treatment of diphenylmercury with an equivalent amount of trimethylgallium resulted in the formation of methyl(diphenyl)gallium (4). The X-ray crystallographic studies of compounds 1, 2, 3, and 4 revealed the presence of trigonal planar coordinate gallium atoms in monomeric molecules, which associate to polymeric strands by additional intermolecular gallium π-aryl contacts, thus leading to an overall trigonal bipyramidal coordination geometry at gallium. Compounds 1-4 are stable in the solid state and in solution. Substituent redistribution reactions take place at higher temperatures and at room temperature in the presence of THF. Compound 1 could also be prepared by the reaction of triphenylgallium with an excess of trimethylgallium at higher temperatures.
- Jutzi, Peter,Izundu, Joseph,Neumann, Beate,Mix, Andreas,Stammler, Hans-Georg
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p. 4565 - 4571
(2009/02/07)
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- Method
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Organometallic compounds of Group IIB and IIIA metals that are substantially pure and contain low levels of oxygenated impurities are provided. Also provided are methods of preparing such organometallic compounds.
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Page/Page column 5
(2010/10/20)
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- Methods for producing trialkyl gallium
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The present invention provides method 1 for producing a trialkyl gallium comprising the steps of reacting gallium, magnesium, and an alkyl halide in an ether, and diluting during the reaction the reaction system with an ether; method 2 for producing a trialkyl gallium comprising the steps of heating in a vacuum a mixture of magnesium and molten gallium, and reacting the mixture with an alkyl halide in a solvent; and method 3 for producing a trialkyl gallium comprising the step of reacting an alkyl metal with an alkylgallium halide compound represented by the formula ???????? Ga2RmX6-m wherein R is a methyl or ethyl group, X is a halogen atom, and m is an integer from 1 to 5.
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- Preparation of high purity alkyl gallium
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Trialkylgallium is prepared by reacting a gallium halide or alkyl gallium with trialkylaluminum in a solvent having a boiling point which is at least 10°C higher than the boiling point of the trialkylgallium, such as mesitylene or o-dichlorobenzene. High purity alkyl gallium is obtained in high yields.
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- Purification of metal Hydrocarbon
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A contaminated Group III metal hydrocarbon is purified by providing an adduct of Group III metal hydrocarbon with a Lewis base in a solvent having a boiling point which is up to 200°C, but at least 30°C higher than the boiling point of the Group III metal hydrocarbon, separating the solvent from the adduct, and heating the adduct for thermal dissociation, thereby releasing the Group III metal hydrocarbon in high purity form.
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- Preparation of organometal compounds
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A method of preparing organometal compounds that does not use oxygenated solvents is provided. The compounds produced by such method are particularly useful as precursor compounds for metalorganic chemical vapor deposition processes used in the manufacture of electronic devices. Methods of depositing metal films using such organometal compounds are also provided.
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- A digalla[1.1]ferrocenophane and its coordination chemistry: Synthesis and structure of [{Fe(η5-C5H4)2}2 {GaMe}2] and of the adducts [{Fe(η5-C5H4)2}2 {GaMe(D)}2] (D = monodentate donor)
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Gentle warming of 1,1′-bis(dimethylgally)ferrocene (1) leads to the formation of trimethylgallium and the thermolabile compound [{Fe(η5-C5H4)2}2{GaMe }2] (2), a [1.1]ferrocenophane featuring group 13 elements in bridging positions. While NMR data for 2 prove a dynamic structure in solution, X-ray data reveal an anti conformation of the ferrocenophane framework in the solid state. The anti conformation is maintained in the thermolabile adducts 2a-g, which are obtained from 2 and the donors diethyl ether (2a), pyridine (2b), pyrimidine (2c), quinoxaline (2d), DMSO (2e), pyrazine (2f), and dioxane (2g), by donor-exchange reactions (2b-g) or on gentle warming of the respective donor adducts of 1. Rodlike polymers are formed either by interaction of 2 with bidentate donors (2f,g) or by π-stacking effects of aromatic molecules acting as monodentate donors (2b-d). Steric requirements inhibit the complex formation between 2 and the donor phenazine. A cyclic voltammogram of 2b in pyridine reveals two reversible oxidation steps at -314 and -114 mV, indicating only weak electron delocalization in the cationic species. The formation of 2 from 1 has been shown to be reversible and thus is an example of an application of dynamic covalent chemistry as synthetic strategy.
- Althoff, Alexander,Jutzi, Peter,Lenze, Norman,Neumann, Beate,Stammler, Anja,Stammler, Hans-Georg
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p. 2766 - 2774
(2008/10/08)
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- Synthesis and X-ray crystal structure of [Me2GaBi(SiMe3)2]3
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[Me2GaBi(SiMe3)2]3 (1) was synthesized in high yield by the equimolar reaction of Me2GaH and Bi(SiMe3)3 and characterized by mass and multinuclear NMR spectroscopy and by single-
- Thomas, Florian,Schulz, Stephan,Nieger, Martin
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p. 2793 - 2795
(2008/10/08)
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- Syntheses and crystal structures of dialkylgallium hydrides - Dimeric versus trimeric formula units
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Dialkylgallium hydrides (R = Me, Et, iPr, iBu, neopentyl) were obtained on two different synthetic routes. The dimethyl and diethyl compounds were formed by the reaction of LiH with the corresponding dialkylgallium chlorides via lithium dialkyldihydridogallate intermediates, which so far have not been isolated in a pure form. On the second route, trialkylgallium compounds were treated with [GaH3·NMe2Et] to yield the dialkylgallium hydrides by a substituent exchange reaction. The dimethyl, diethyl and diisopropyl compounds are trimeric in solution. That trimeric structure was verified for the diisopropyl derivative by a crystal structure determination. Di(neopentyl)gallium hydride has a dimeric structure in solution and in the solid state.
- Uhl, Werner,Cuypers, Lars,Geiseler, Gertraud,Harms, Klaus,Massa, Werner
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p. 1001 - 1006
(2008/10/08)
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- A simple synthesis of non-solvated trimethylgallium and triethylgallium
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A simple synthesis of non-solvated trimethylgallium and triethylgallium is proposed based on the reaction of alkyl iodides with a mixture or an alloy of magnesium and gallium in the absence of a solvent or in aliphatic hydrocarbons as solvent.
- Zakharkin,Gavrilenko
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p. 1243 - 1247
(2008/10/09)
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- A simple synthesis of non-solvated galliumtrialkyls
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A simple synthesis of non-solvated galliumtrialkyls is proposed based on the reaction of alkyl iodides with a mixture or an alloy of magnesium and gallium in the absence of a solvent or in aliphatic hydrocarbons.
- Zakharkin,Gavrilenko,Fatyushina
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p. 379 - 380
(2007/10/03)
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- Process for the preparation of trialkyl compounds of group 3a metals
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Process for the preparation of trialkyl compound of a Group 3a metal, in which a Group 3a metal is contacted with an alkyl halide in the presence of an alkali metal to obtain a trialkyl compound of the Group 3a metal and alkali-metal halide.
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- Ligand redistribution reactions of Me2Ga(C5H5) and MeGa(C5H5)2
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The compounds Me2Ga(C5H5) and MeGa(C5H5)2 have been prepared by ligand redistribution reactions between appropiate stoichiometric quantities of Ga(C5H5) and GaMe3.Both compounds have been demonstrated by 1H NMR spectral studies to be unstable in solution and to form symmetrized products by ligand redistribution reactions.Thus, Me2Ga(C5H5) forms GaMe3 and MeGa(C5H5)2 as primary products whereas MeGa(C5H5)2 decomposes to Ga(C5H5)3 and Me2Ga(C5H5).The compound Me2Ga(C5H5) has also been shown to serve as a cyclopentadienyl transfer reagent as it reacts with FeCl2 to form Fe(C5H5)2 and Me2GaCl.
- Beachley, O. T.,Royster, T. L.,Arhar, J. R.
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- Vibrational spectra of trimethyl gallium species in relation to the force field and methyl group internal rotation
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Infrared and Raman spectra are reported for Ga(CH3)3, Ga(CD3)3 and Ga(CHD2)3 in the gas phase.These were also examined in the i.r. spectrum in the solid phase at 78 K.The new Raman spectra of the CHD2 species strongly support earlier i.r. evidence for CH force constant variation during free internal rotation of the methyl groups, from the presence of two bands at 2940 (vs) and 2922 cm-1 (w) identified as due to νisav and νis respectively.The observed a' and e' frequencies of the d0 and d9 species are used to obtain a force field in which three interaction constants are well defined.The best value of the Ga-C stretching force constant is 2.356(28) mdyn Angstroem-1.In the crystal phase at 78 K, the e' modes due to δs Me and νas GaC3 are split, indicating a site group symmetry lower than C3.Gallium and carbon isotope frequency shifts are predicted.
- McKean, D. C.,McQuillan, G. P.,Duncan, J. L.,Shephard, N.,Munro, B.,et al.
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p. 1405 - 1412
(2007/10/02)
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- Electrochemical Studies of Group 3 Alkyl Derivatives. Part 1. Synthesis of Trimethylgallium Adducts
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Electrolysis of dimethylmagnesium in tetrahydrofuran (thf) with a gallium anode yields the adduct GaMe3*thf directly; the trialkylamine and trialkylphosphine adducts GaMe3 * L (L = NEt3, PMe3, or PEt3) are obtained by direct addition of an excess of L to GaMe3*thf.Free GaMe3 is obtained by reaction of MeI with a Mg-Ga alloy in an ether solvent.
- Jones, Anthony C.,Cole-Hamilton, David J.,Holliday, A. Kenneth,Ahmad, M. Munir
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p. 1047 - 1050
(2007/10/02)
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