Iodotrimethylplatinum(IV)

Abstract

To provide a method by which trimethylplatinum(IV) iodide with a high degree of purity, in particular, substantially free of impurities of magnesium salts, sodium salts, potassium salts and elemental iodine, can be produced easily, cost-effectively and reproducibly at good yields, including space-time yields.SOLUTION: A method for producing trimethylplatinum(IV) iodide comprises a reaction of at least one platinum compound, which is selected from the group consisting of platinum(II) compounds and platinum(IV) compounds, with at least one methyl Grignard compound according to the general formula MeMgX (where X are independently selected from the group consisting of Cl, Br and I) and iodomethane in an aprotic polar solvent SA comprising an ether SE and a halogenated hydrocarbon SH, where the molar ratio of Pt metal:MeMgX:iodomethane is between 1:4:4 and 1:6:6.SELECTED DRAWING: None

Description

[Technical Field]

[0001] Iodotrimethylplatinum(IV) (Me3PtI), methods for its preparation, and its uses are known. [Background technology]

[0002] Iodotrimethylplatinum(IV) is used, for example, as a reactant for preparing various platinum(IV) complexes, such as (cyclopentadienyl)trimethylplatinum(IV) and its derivatives, the latter of which is used, inter alia, as a platinum precursor in atomic layer deposition (ALD), metalorganic chemical vapor deposition (MOCVD), or metalorganic chemical vapor phase epitaxy (MOVPE) for the deposition of platinum or platinum-containing layers.

[0003] In 1909, Pope and Peachey (J. Chem. Soc. 1909, 95, 571) first reported the synthesis of platinum(IV) compounds starting from anhydrous platinum(IV) chloride and a large excess of the Grignard reagent methylmagnesium iodide (MeMgI). Essentially, three methods for preparing iodotrimethylplatinum(IV) are known in the prior art: a. A method of reacting the dimethylplatinum(II) compound Pt(L)Me2 (where L = COD = 1,5-cyclooctadiene or L = NBD = bicyclo[2.2.1]heptane-2,5-dienyl) with iodomethane (MeI) in benzene (HC Clark and LE Manzer, J. Organomet. Chem. 1972, 38, C41-C42; TG Appleton et al., J. Organomet. Chem. 1986, 303, 139-149), b. A method in which a platinum(II) compound, such as anhydrous Zeise salt K[(C2H4)PtCl3], is reacted with the Grignard reagent MeMgI in a diethyl ether / benzene mixture as the solvent (Hel'man, Gorushkina, Doklady Akad. Nauk, SSSR 1947, 57, 259-261), and c. Platinum(IV) compounds, such as PtCl4 (H. Gilman et al., J. Am. Chem. Soc. 1953, 75, 2063-2065), K2PtCl6 (LD Boardman and RA Newmark, Magnetic Resonance in Chemistry 1992, 30, 481-489) or (NH4)2[PtCl6] (VM Kharchevnikov, Zhurnal Obshchei Khimii 1973, 43, 817-821), with the Grignard reagent MeMgI in a diethyl ether / benzene mixture; or the Grignard reagent MeMgI, prepared starting from magnesium and excess MeI in a diethyl ether / benzene mixture (e.g., D.E. Cregg and J.R. Hall, Inorganic Syntheses 1967, 10, 71-74); or Reaction with methyllithium (MeLi) in a diethyl ether / tetrahydrofuran mixture followed by the addition of saturated potassium iodide solution (see, for example, L.D. Boardman and R.A. Newmark, Magnetic Resonance in Chemistry 1992, 30, 481-489).

[0004] One drawback of the synthetic route for the preparation of Me3PtI given in a. is that it is labor-intensive and costly due to the overall three-step process. The first step is to prepare Pt(L)Cl2, which in the second step reacts with MeLi to form Pt(L)Me2. The latter then reacts with MeI to form Me3PtI. The reaction of Pt(NBD)Me2 with MeI in benzene provides highly pure iodotrimethylplatinum(IV) (white solid) in very good yield (97%) (T.G. Appleton et al., J. Organomet. Chem. 1986, 303, 139-149).

[0005] In the simplest case, only one synthetic step is required within the synthetic routes b and c, but at least one one-pot method is possible. However, the respective methylation reagents, i.e., Grignard reagents, and optionally additional iodomethane or methyllithium, are usually used in relatively large excess amounts relative to the amount of Pt metal used. For example, molar ratios of Pt metal:MeMgI of 1:4.2 and 1:5, molar ratios of Pt metal:MeMgI:MeI of 1:4.6:3.2, 1:7:4.5, and 1:11:8.4, and molar ratios of Pt metal:MeLi of at least 1:8, for example, 1:8.2 are provided. From an (atomic) economic and ecological point of view, this is disadvantageous, especially because satisfactory results are not obtained in terms of yield and / or product purity, as can already be seen, especially from the color of the product. When a relatively small excess of the Grignard reagent MeMgI is used, relatively strong coloration and / or relatively low yields of iodotrimethylplatinum(IV) have been reported (see H. Gilman et al., J. Am. Chem. Soc. 1953, 75, 2063-2065: Pt metal:MeMgI molar ratio is 1:4.2; GIZharkova et al., Olyhedron 2012, 40, 40-45: Pt metal:MeMgI molar ratio is 1:5). According to the protocol by Hel'man and Gorushkina, iodotrimethylplatinum(IV) is obtained in the form of orange crystals in approximately 70% yield using MeMgI and MeI (Doklady Akad. Nauk, SSSR 1947, 57, 259-261: Pt metal:MeMgI:MeI molar ratio is 1:4.6:3.2).Addition of MeI or use of a relatively large excess of the methylating reagent MeLi, or even a larger excess of the Grignard reagent MeMgI, resulted in lighter isolated iodotrimethylplatinum(IV) in moderate to good yields ranging from 70% to 89% in each case (see J.C.Baldwin and W.C.Kaska, Inorg. Chem. 1975, 14, 2020: Pt metal:MeMgI:MeI molar ratio is 1:11:8.4; D.C. Legg and J.R.Hall, Inorganic Syntheses 1967, 10, 71-74: Pt metal:MeMgI:MeI molar ratio is 1:7:4.5; L.D. Boardman and R.A. Newmark, Magnetic Resonance in Chemistry 1992, 30, 481-489: Pt metal:MeLi molar ratio is 1:8.2).

[0006] Iodotrimethylplatinum(IV) can be obtained in very different colors by the preparation methods described in the prior art. Thus, the platinum(IV) compound has been described, inter alia, as a white (T.G. Appleton et al., J. Organomet. Chem. 1986, 303, 139-149), yellow (D.E. Cregg and J.R. Hall, Inorganic Syntheses 1967, 10, 71-74), and orange solid (G.I. Zharkova et al., Polyhedron 2012, 40, 40-45; orange crystals: Hel'man, Gorushkina, Doklady Akad. Nauk, SSSR 1947, 57, 259-261). The variation in the visual appearance of the isolated product indicates a wide range of product quality or purity. According to Hoff and Brubaker (Inorg. Chem. 1968, 7, 1655-1656), iodotrimethylplatinum(IV) exists in the solid state as the tetramer [Me3PtI]4, regardless of whether it is obtained as a white or yellow solid. The authors hypothesize that the yellow coloration is due to slight contamination with iodine.

[0007] Furthermore, the yields achieved by known synthetic routes vary widely. Prior art specifications range from 45% (H. Gilman et al., J. Am. Chem. Soc. 1953, 75, 2063-2065) to 97% (T. G. Appleton et al., J. Organomet. Chem. 1986, 303, 139-149). According to Kharchevnikov (Zhurnal Obshchei Khimii 1973, 43, 817-821), when the molar ratio of (NH)PtCl:MeMgI increases from 1:2 to 1:15, the total yield of iodotrimethylplatinum(IV), i.e., the combined total yield of dimer [MePtI] and tetramer [MePtI], increases from 12% to 86%. Additionally, Kharcevnikov reported that the yield decreased from 87% to 8% when the molar fraction of diethyl ether in the diethyl ether / benzene mixture used increased from 0.15 to 1.0. Furthermore, Boardman and Newmark (Magnetic Resonance in Chemistry 1992, 30, 481-489) reported that the reaction of K2[PtCl6] with MeLi not only required the use of a large excess of the methylating reagent, but also required the maintenance of relatively low temperatures. Thus, the use of less than 8 molar equivalents of MeLi or reaction temperatures above 5-10°C resulted in significant yield losses.

[0008] The drawback of the aforementioned synthetic routes is that the achieved product units and yields are mostly insufficient and in part not reproducible. This may be due to the formation of by-products that can only be partially or completely removed with difficulty. Furthermore, the reaction of the respective raw material with silver sulfate and the subsequent addition of potassium iodide is required to purify iodotrimethylplatinum(IV), which is regularly obtained in a relatively lower quality and, in particular, more or less strongly colored due to iodine contamination (DEClegg and JR Hall, Inorganic Syntheses 1967, 10, 71-74).

[0009] Therefore, according to the prior art described herein, the preparation of iodotrimethylplatinum(IV) with sufficient purity and yield is only possible, particularly by the route mentioned under a), at a relatively high effort and cost.

[0010] Overall, the synthetic routes known from the literature for the preparation of iodotrimethylplatinum(IV) are classified as unsatisfactory from an ecological and (atomic) economic point of view. One important reason is that the selectivity of the obtained iodotrimethylplatinum(IV) is often relatively low, resulting in a low yield, e.g., a low space-time yield, and / or a low purity. The term "space-time yield" refers to the amount of product formed per space and time in the reaction vessel or reactor. Summary of the Invention [Problem to be solved by the invention]

[0011] Therefore, the object of the present invention is to overcome these and other disadvantages of the prior art and to provide a method for easily, cost-effectively, and reproducibly producing iodotrimethylplatinum(IV) with high purity, in particular substantially free of impurities due to magnesium salts, sodium salts, potassium salts, and elemental iodine, in good yield (including space-time yield). In particular, the purity of iodotrimethylplatinum(IV) should meet the requirements set for catalysts, precatalysts, and for reactants for producing precursors for chemical vapor deposition processes. The method should further be capable of being carried out on an industrial scale with comparable yields and purities of iodotrimethylplatinum(IV), and be characterized by reduced or avoided formation of by-products that are difficult to separate or cannot be separated at all. The invention further relates to iodotrimethylplatinum(IV) obtainable or obtained according to the claimed method, as well as to its uses. In addition, the method for producing a platinum(IV) compound allows the compound to be easily, cost-effectively, and reproducibly produced with high purity and good yield (including space-time yield). The platinum(IV) compound can be obtained according to the claimed method or can be prepared using the obtained iodotrimethylplatinum(IV). Furthermore, the subject of the invention is a substrate having at least one platinum layer or one platinum-containing layer on at least one surface. Each layer should be obtainable according to the claimed method or can be produced using the obtained platinum(IV) compound. The invention also relates to a method for producing an electrode for an electronic component or a fuel cell using the platinum(IV) compound obtained or obtainable according to the method claimed herein. [Means for solving the problem]

[0012] The main features of the invention are defined in the claims.

[0013] The goal is Ether S E and halogenated hydrocarbons S H aprotic polar solvent S containing Awherein at least one platinum compound selected from the group consisting of platinum (II) compounds and platinum (IV) compounds is at least one methyl Grignard compound according to the general formula MeMgX, where X is independently selected from the group consisting of Cl, Br, and I; and This can be achieved by a method for producing iodotrimethylplatinum(IV), which comprises reacting Pt metal, MeMgX, and iodomethane in a molar ratio of Pt metal:MeMgX:iodomethane of 1:4:4 to 1:6:6. DETAILED DESCRIPTION OF THE INVENTION

[0014] In the context of the present invention, the expression "iodotrimethylplatinum(IV)" includes all solvent-free molecular formulae of the platinum(IV) compound in question, in particular Me3PtI, and the solvent-free molecular formulae of the oligomers [Me3PtI]2 and [Me3PtI]4.

[0015] The "at least one platinum compound" can also be a mixture comprising at least two platinum compounds selected from the group consisting of platinum(II) compounds and platinum(IV) compounds.

[0016] The order in which the reaction vessel is charged with the reactants, i.e., at least one platinum compound, a methyl Grignard compound of general formula MeMgX, and iodomethane, can be freely selected, and does not affect the success of the reaction, and in particular the purity and yield of iodotrimethylplatinum(IV) obtained or obtainable using this method, in solution or as a solid.

[0017] The terms "reaction vessel" and "reaction vessel" in the context of the present invention are used interchangeably and are not limited by volume, material composition, equipment, or form. Suitable reaction vessels include, for example, glass flasks, enamelled reactors, stirred tank reactors, pressure vessels, tubular reactors, microreactors, and flow reactors.

[0018] The methods for producing iodotrimethylplatinum(IV) described herein can be carried out as a discontinuous process or as a continuous process.

[0019] Aprotic polar solvent S A Also, two or more ethers S E and / or two or more halogenated hydrocarbons S H One embodiment of the method may also be a solvent mixture containing at least one ether S E and at least one halogenated hydrocarbon S H The aprotic polar solvent S is miscible with A is at least one ether S E and at least one halogenated hydrocarbon S H The solvent may include a further aprotic polar solvent that is miscible with the solvent.

[0020] In the context of the present invention, two solvents are said to be miscible if they are miscible, ie, do not exist as two phases, at least during the respective reactions.

[0021] Compared to prior art methods, the method described herein achieves improved product quality, i.e., product purity, while simultaneously increasing yields (including space-time yields). Surprisingly, very high product purity is achieved, even though the methylating reagent of general formula MeMgX is used in a relatively small excess relative to the amount of platinum metal used, along with the addition of iodomethane. This is particularly surprising in light of previously known methods for the preparation of iodotrimethylplatinum(IV). As explained above, for a similar molar ratio of Pt metal:MeMgI:MeI, i.e., 1:4.6:3.2, the prior art describes iodotrimethylplatinum(IV) being isolated after a relatively complex recrystallization from hot benzene in the form of orange crystals, with a moderate yield of approximately 70%. Only when the Grignard reagent MeMgI was used in significantly larger excess, which was unfavorable from an (atomic) economic and ecological point of view, did the pale iodotrimethylplatinum(IV) be isolated in moderate to good yields, sometimes between 70% and 89%, when MeI was added.

[0022] In contrast to previously known synthetic strategies, in the method described herein, a relatively small excess of methylating reagent is sufficient to obtain and / or isolate iodotrimethylplatinum(IV) with very high purity in nearly quantitative yield. Thus, for example, when K2[PtCl6] is reacted with MeMgI and MeI in a molar ratio of Pt:MeMgI:MeI of 1:5:5 and a diethyl ether / dichloromethane mixture is used in a volume ratio of 0.86:1, the target compound is obtained as an off-white, partially crystalline powder in approximately 98% yield. The iodotrimethylplatinum(IV) obtained or obtainable by the method claimed herein as an isolated solid or in solution is free of impurities or contains little or no impurities introduced by salts produced during its preparation. In particular, the content of magnesium salts and potassium and / or sodium salts is significantly lower. The magnesium content of the isolated product iodotrimethylplatinum(IV) measured in the above examples by ICP-OES was <300 ppm, and the potassium content measured by ICP-OES was <50 ppm. Typically, impurities caused by elemental iodine can be identified visually, i.e., based on a characteristic yellow, orange, red, or brown color as the iodine content increases. However, iodotrimethylplatinum(IV) isolated by the methods claimed herein generally exists as an off-white or white powder that is at least semi-crystalline or in the form of off-white or white crystals, such that the iodine impurity is present at only trace levels. Thus, iodotrimethylplatinum(IV) obtained or obtainable by the methods described herein is referred to as "substantially free of elemental iodine impurities."

[0023] The claimed method also differs from the methods disclosed in the prior art by the choice of solvent: ether S, instead of the commonly used diethyl ether / benzene mixture, is used. E and halogenated hydrocarbons S H aprotic polar solvent S containing A is provided here. Ether SE : Halogenated hydrocarbons S H may be, for example, from 0.5:1 to 1:5, advantageously from 0.75:1 to 1:4, in particular from 0.85:1 to 1:3.

[0024] Aprotic polar solvent S A This is particularly advantageous because salts typically obtained as by-products, such as NaCl, KCl, MgCl, and MgI, have relatively low solubility. Quantitative or nearly complete separation of the salt load can therefore be achieved by work steps that can be carried out quickly and easily, i.e., by filtration, centrifugation, and / or decantation. Subsequently, the filtrate, centrifugate, or decantate can advantageously and optionally be subjected to further purification and / or isolation steps, which can be carried out quickly and without complexity and without special preparation efforts, in particular without ensuring an inert gas atmosphere. Overall, purification and / or isolation of the product is relatively simple.

[0025] In summary, it should be noted that iodotrimethylplatinum(IV) can be produced in a simple, cost-effective, and reproducible manner using the method claimed herein. The target compound is obtained in very good yields (including space-time yields) with very high purity, in particular substantially free of impurities from magnesium, sodium, and potassium salts and elemental iodine. The formation of by-products that are difficult to separate or cannot be separated at all, in particular elemental iodine, is advantageously reduced or completely avoided. Depending on the selected solvent mixture, the salt load produced, for example, in the form of NaCl, KCl, MgCl, or MgI, can advantageously be completely or almost quantitatively separated. The purity of iodotrimethylplatinum(IV) thus obtained or obtainable therefore meets the requirements set for reactants for producing catalysts, precatalysts, and precursors for chemical vapor deposition processes. In addition, the methods described herein can also be carried out on an industrial scale, and iodotrimethylplatinum(IV) can be or is obtained in comparable yields (including space-time yields) and purities.

[0026] Overall, the process claimed herein for the preparation of iodotrimethylplatinum(IV) is classified as satisfactory from an ecological and (atomic) economic point of view.

[0027] In the context of the present invention, the expression "substantially free from impurities due to magnesium salts" refers to a magnesium content in the isolated product iodotrimethylplatinum(IV) of ≦500 ppm, ideally ≦300 ppm. The expression "substantially free from impurities due to potassium salts" refers to a potassium content of ≦100 ppm, ideally ≦50 ppm; the same applies to the expression "substantially free from impurities due to sodium salts." In the context of the present invention, the expression "substantially free from impurities due to elemental iodine" is used in particular with respect to isolated iodotrimethylplatinum(IV) that is present as an off-white or white, optionally at least semi-crystalline, powder or in the form of off-white or white crystals.

[0028] In one embodiment of the method for producing iodotrimethylplatinum(IV), the at least one platinum compound is a platinum(II) salt or a platinum(IV) salt, wherein platinum(II) or platinum(IV) is contained in the cation or anion. Advantageously, the at least one platinum compound is a platinum(IV) salt, wherein platinum(IV) is contained in the cation or anion.

[0029] In a further variation of the method, at least one platinum halide or at least one haloplatinate is provided. According to another embodiment, at least one platinum compound is provided selected from the group consisting of PtX2, [(C2H4)PtX2]2, M[(C2H4)PtX3], M2[PtX4], PtX4, M2[PtX6], their derivatives and isomers, and mixtures thereof. In this case, X is independently selected from the group consisting of F, Cl, Br, and I, preferably Cl, Br, and I, especially Cl and Br. M is independently selected from the group consisting of alkali metals, preferably lithium, sodium, or potassium, especially sodium or potassium; alkaline earth metals, preferably magnesium, calcium, strontium, or barium, especially magnesium or calcium; and silver. In another variation of the claimed method, at least one platinum chloride or one chloroplatinate is provided. In a further embodiment, there is provided at least one platinum compound selected from the group consisting of PtCl2, [(C2H4)PtCl2]2, K[(C2H4)PtCl3], Na2[PtCl4], K2[PtCl4], PtCl4, Na2[PtCl6], and K2[PtCl6], derivatives and isomers thereof, and mixtures thereof. According to yet another variation, there is provided at least one platinum compound selected from the group consisting of PtCl4, Na2[PtCl6], and K2[PtCl6], derivatives and isomers thereof, and mixtures thereof. In yet another variation, there is provided at least one platinum compound selected from the group consisting of Na2[PtCl6] and K2[PtCl6], derivatives and isomers thereof, and mixtures thereof.

[0030] Another embodiment variation of the process for producing iodotrimethylplatinum(IV) provides that the at least one methyl Grignard compound comprises or is MeMgI. Selection of platinum compound(s), solvent S A , platinum concentration, reaction temperature and / or reaction pressure, batch size, ether S E : Halogenated hydrocarbons S H Depending on the selection of other reaction conditions, such as the choice of the intended volume ratio of MeMgl, the use of MeMgl may be advantageous to allow better control over the course of the reaction, especially the exotherm.

[0031] In yet another variation, the aprotic polar solvent S A is chemically inert. In the context of the present invention, the term "inert solvent" means a solvent that is not chemically reactive under the respective process conditions. Under the respective reaction conditions, including purification and / or isolation steps, the inert solvent therefore does not react with potential reaction partners, in particular reactants and / or intermediates and / or products and / or by-products, and also with other solvents, air, or water.

[0032] In a further embodiment, the aprotic polar solvent S A is the boiling point T A and has a boiling point T A The boiling point T is between 30℃ and 140℃. A The temperature is preferably 31°C to 120°C, in particular 32°C to 110°C, or 33°C to 99°C. A can be quantitatively removed, for example, by simply applying negative pressure to each reaction vessel and, optionally, by slightly increasing the temperature of each reaction mixture.

[0033] According to another embodiment of the method, the halogenated hydrocarbon S H is selected from the group consisting of alkyl halides and aromatic halogenated hydrocarbons. Advantageously, the halogenated hydrocarbon S H are chlorinated or brominated hydrocarbons. In particular, halogenated hydrocarbons S His selected from the group consisting of dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, dibromomethane, 1,1-dibromoethane, 1,2-dibromoethane, chlorobenzene, and isomers thereof, and mixtures thereof. Another embodiment of the method for producing iodotrimethylplatinum(IV) is the ether S E is selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, 1,4-dioxane, diethyl ether, methyl tert-butyl ether, di-n-propyl ether, diisopropyl ether, cyclopentyl methyl ether, and isomers thereof, and mixtures thereof. Advantageously, all of the aforementioned solvents are solvents commonly used in the chemical industry. Furthermore, the solvents have a boiling point of <140°C, in some cases <110°C, or <100°C. Quantitative removal of the solvent is therefore possible, for example, by simply applying negative pressure to each reaction vessel and, optionally, by slightly increasing the temperature of each reaction mixture.

[0034] In another embodiment of the method for producing iodotrimethylplatinum(IV), the molar ratio of Pt metal:MeMgX:iodomethane is 1:4.05:4.05 to 1:5.9:5.9, or 1:4.1:4.1 to 1:5.5:5.5, or exactly 1:5:5. In a further embodiment variant of the method, the molar ratio of MeMgX:iodomethane is 1:1.5 to 1.5:1, or 1:1.4 to 1.4:1, advantageously 1:1.3 to 1.3:1, or 1:1.2 to 1.2:1, in particular 1:1.1 to 1.1:1, or exactly 1:1.

[0035] According to another embodiment of the method, the reaction comprises the following steps: A. Providing at least one platinum compound; B. At least one platinum compound from step A. reacting with iodomethane and at least one methyl Grignard compound of general formula MeMgX; Includes:

[0036] Another variation of the method described herein is where the reaction comprises the following steps: i) providing at least one platinum compound, in particular as a suspension or as a solid; ii) adding iodomethane; iii) adding at least one methyl Grignard compound according to the general formula MeMgX; The present invention provides a method for manufacturing a semiconductor device, comprising:

[0037] In this case, the at least one methyl Grignard compound is usually reacted with at least one platinum compound during and / or after step iii).

[0038] Another embodiment of the method is characterized in that in step i) the suspension of at least one platinum compound is dissolved in a halogenated hydrocarbon S H Alternatively, the feed may be prepared in a solvent such as dichloromethane or in a halogenated hydrocarbon or mixture of halogenated hydrocarbons that is miscible therewith. E For example, it may be provided in diethyl ether or in an ether or ether mixture that is miscible therewith. H may also constitute a solvent mixture, i.e., may contain several halogenated hydrocarbons. E Alternatively, at least one platinum compound may be provided in a solvent mixture comprising one or more halogenated hydrocarbons and one or more ethers. In particular, the solvent mixture may comprise an aprotic polar solvent S A In yet another variation of the method, the at least one platinum compound is miscible with or identical to the aprotic polar solvent S A It is provided that the compound is provided as a suspension in an aprotic polar solvent that is miscible with the compound.

[0039] Iodomethane is an ether S EFor example, the halogenated hydrocarbon S may be added as a solution in di-n-propyl ether or as an ether or mixture of ethers that are miscible therewith. H For example, it is possible to add iodomethane in dibromomethane or in a halogenated hydrocarbon or mixture of halogenated hydrocarbons that are miscible with it. H The ether S may also comprise a mixture containing several halogenated hydrocarbons. E can also be a mixture of ethers. According to another variant of the method, iodomethane is dissolved in an aprotic polar solvent S A Medium or aprotic polar solvent S A The iodomethane is added in an aprotic polar solvent or solvent mixture that is miscible with the iodomethane. Alternatively, the iodomethane can be added substantially, i.e., as a liquid.

[0040] Methyl Grignard compounds are usually ethers or ether mixtures S E The Grignard solution used, i.e., the respective ether or ether mixture S, is added as a solution in the Grignard solution or as an ether or ether mixture miscible therewith. E The molar concentration of the methyl Grignard compound in the ether or ether mixture miscible therewith advantageously depends on the remaining reaction conditions, for example the choice of platinum compound(s), the choice of the further aprotic polar solvent or solvent mixture used, in particular the halogenated hydrocarbon or halogenated hydrocarbon mixture S H Selection of reaction temperature and / or reaction pressure, selection of platinum concentration, selection of batch size, ether S E : Halogenated hydrocarbons S H The selection is made taking into account the intended volume ratio of

[0041] Each reactor may also be charged with the reactants, ie, at least one platinum compound, a methyl Grignard compound of general formula MeMgX, and iodomethane, in a different order.

[0042] Therefore, another embodiment of the method is characterized in that in step ii) at least one methyl Grignard compound according to the general formula MeMgX is an ether or ether mixture S E In step iii), the ether S is added as a solution in water or as an ether or ether mixture that is miscible therewith. E For example, iodomethane may be added as a solution in methyl tert-butyl ether, or as an ether or mixture of ethers with which it is miscible. Alternatively, the halogenated hydrocarbon S H It is possible to add iodomethane in a halogenated hydrocarbon, for example in chlorobenzene, or in a halogenated hydrocarbon or mixture of halogenated hydrocarbons that are miscible with it. H The ether S may also comprise a solvent mixture containing several halogenated hydrocarbons. E can also be a mixture of ethers. According to another variant of the method, iodomethane is dissolved in an aprotic polar solvent S A Medium or aprotic polar solvent S A The iodomethane is added in an aprotic polar solvent or solvent mixture that is miscible with the iodomethane. Alternatively, the iodomethane can be added substantially, i.e., as a liquid.

[0043] In yet another variant of the method, iodomethane and at least one methyl Grignard compound according to the general formula MeMgX are added in a single step. The methyl Grignard compound is firstly dissolved in an ether or ether mixture S using a corresponding excess of iodomethane. E Alternatively, the methyl Grignard compound may be prepared in situ in a pre-prepared and / or stored, optionally commercially available, ether or ether mixture S EThe methyl Grignard compound may be used as a solution in an ether or in an ether or mixture of ethers miscible therewith, to which the intended amount of iodomethane is added before the addition of the solution of at least one methyl Grignard compound, or the methyl Grignard compound and iodomethane are added separately but simultaneously.

[0044] As used herein, the phrase "prepared in situ" means that the reactants necessary for the synthesis of the compound so prepared are reacted in suitable stoichiometric amounts in a solvent or solvent mixture, and the resulting product is not isolated. Instead, the solution or suspension containing the compound prepared in situ is generally reused directly, i.e., without isolation and / or further purification.

[0045] A further embodiment of the method provides that at least one methyl Grignard compound according to the general formula MeMgX is provided in step i) and in step ii) at least one platinum compound is added, in particular in the form of a suspension or substantially, i.e. as a solid. The methyl Grignard compound is first dissolved in a corresponding excess of iodomethane to give an ether or ether mixture S E Alternatively, the methyl Grignard compound may be prepared in situ in a pre-prepared and / or stored, optionally commercially available, ether or ether mixture S E The platinum compound may be used as a solution in an ether or ether mixture miscible therewith, to which a predetermined amount of iodomethane is added before the addition of the solution of at least one methyl Grignard compound. In yet another variation, the methyl Grignard compound and iodomethane are added separately but simultaneously. Alternatively or additionally, iodomethane may be added in portions before and / or during and / or after the addition of the at least one platinum compound.

[0046] According to another variant of the method, the at least one platinum compound is provided or added using an injection device, in particular as a solid through a funnel or as a suspension by dropwise addition or injection. Alternatively or additionally, shut-off and / or stop valves can be provided in the feed lines of the reactor.

[0047] A further embodiment of the method provides that at least one methyl Grignard compound of the general formula MeMgX and / or iodomethane is added or dispensed using an injection device. The addition can be carried out, for example, by dropwise addition or injection. Alternatively or additionally, shut-off and / or stop valves can be provided in the feed lines of the reactor.

[0048] Furthermore, the reaction of at least one platinum compound with iodomethane and a methyl Grignard compound of general formula MeMgX is carried out at a temperature T U In aprotic polar solvent S A In this case, a method variant is provided in which the temperature T U The reaction temperature T is between -10°C and 140°C, preferably between -5°C and 120°C, and in particular between 0°C and 110°C, or between 0.5°C and 100°C. U In a particularly energy-efficient variant of the method, the temperature T U is 10°C to 50°C, particularly 15°C to 45°C, for example, 20°C, 25°C, 30°C, 35°C, or 40°C.

[0049] Yet another embodiment of the method comprises adding iodomethane and / or at least one methyl Grignard compound according to the general formula MeMgX to the at least one platinum compound at a temperature T C is between −10° C. and 120° C., advantageously between −5° C. and 110° C., in particular between 0° C. and 100° C. During and / or after the addition of iodomethane and / or at least one methyl Grignard compound of the general formula MeMgX, the temperature T CIt is particularly advantageous for the temperature T to be between 0.5° C. and 99° C., advantageously between 1° C. and 90° C., in particular between 2° C. and 80° C. In a particularly energy-efficient variant of the method, during and / or after the addition of iodomethane and / or at least one methyl Grignard compound of the general formula MeMgX, the temperature T C is between 10°C and 50°C, in particular between 15°C and 45°C, for example 20°C, 25°C, 30°C, 35°C or 40°C. According to a further variant of the method, the above temperature ranges are also provided when the charging of each reaction vessel with the reactants, i.e. the addition of the reactants, i.e. the at least one platinum compound, iodomethane and at least one methyl Grignard compound, as described above, is carried out in a different order. In particular, even if at least one methyl Grignard compound of the general formula MeMgX is provided in step i), the at least one platinum compound is added in step ii), in particular in the form of a suspension or substantially, i.e. as a solid.

[0050] In another embodiment of the method, the temperature T U and temperature T C is regulated and / or controlled using a heat transfer medium W. For this purpose, for example, a cryostat containing a heat transfer medium W can be used, which can ideally function both as a coolant and as a heat transfer medium. By using a heat transfer medium W, a defined setpoint value T S1 Temperature T from U any deviation in and the defined setpoint value T S2 Temperature T from C Deviations in temperature T can be largely quenched or compensated for. Typical device deviations cause U and T C By using the heat transfer medium W, the reaction of at least one platinum compound with iodomethane and a methyl Grignard compound of the general formula MeMgX can be carried out in the presence of an aprotic polar solvent S at least in a preselected temperature range or in a plurality of preselected temperature ranges. AFor example, the selection of platinum compound(s), the selection of the concentration of the Grignard solution, the solvent S A Selection of platinum concentration, selection of reaction pressure, selection of batch size, ether S E : Halogenated hydrocarbons S H It may be advantageous to create a temperature program to even better control the course of the reaction or exotherm as a function of other reaction parameters, such as the choice of the intended volume ratio of the platinum compound and the methyl Grignard compound. For example, a lower temperature or a lower temperature range can be selected during the first phase of the reaction of the at least one platinum compound with iodomethane and the methyl Grignard compound than during the second phase of the reaction of the at least one platinum compound with iodomethane and the methyl Grignard compound. It is also possible to provide three or more phases of reaction and / or addition, and thus three or more preselected temperatures or temperature ranges. The choice of platinum compound(s), the choice of the concentration of the Grignard solution, the choice of the solvent S, etc. A Selection of platinum concentration, selection of reaction pressure, selection of batch size, ether S E : Halogenated hydrocarbons S H Depending on the selection of other reaction conditions, such as the selection of the intended volume ratio of the reactants, a heat transfer medium W may be used to maintain the temperature T during and / or after the addition of one of the reactants. C It may be preferable to increase the temperature T using the heat transfer medium W. In this way, it is possible to optionally ensure that the reaction occurs quantitatively. U The increase can last, for example, from 10 minutes to 24 hours.

[0051] Another embodiment of the method for producing iodotrimethylplatinum(IV) provides that the reaction occurs in an inert gas atmosphere.

[0052] In yet another embodiment of the method, a step is carried out after the reaction, which comprises quenching any unreacted methyl Grignard compound of the general formula MeMgX.

[0053] In the context of the present invention, the term "quenching" refers to the inactivation of one or more unreacted methyl Grignard compounds with the general formula MeMgX. A reagent provided for this purpose is hereinafter referred to as a "quencher." One embodiment of the method provides that the quencher is selected from the group consisting of alkyl halides, ketones, alcohols, water, mineral acids, and organic acids, in particular carboxylic acids. Advantageously, the quencher is selected from the group consisting of acetone, 1-bromo-2-chloroethane, 1-bromo-2-fluoroethane, and iodomethane. In particular, the quencher comprises acetone and / or iodomethane. For example, when an excess of iodomethane is used relative to the methyl Grignard compound MeMgX, the use of the above-mentioned additional quencher may be optional, partially, or completely omitted.

[0054] When iodotrimethylplatinum(IV) is prepared according to the methods described herein, the desired target compound, iodotrimethylplatinum(IV), solvent S A and defined, easily separable by-products, such as NaCl, KCl, MgCl, and MgI, are present after the reaction of at least one platinum compound with iodomethane and at least one methyl Grignard compound of the general formula MeMgX. The suspension containing the target compound iodotrimethylplatinum(IV) in solution can be reacted directly with one or more further reactants, such as cyclopentadienyl sodium.

[0055] Or after the reaction: Iodotrimethylplatinum(IV) and aprotic polar solvents S A As a solution containing or As a solid, A step is carried out which includes isolating the iodotrimethylplatinum(IV).

[0056] In a further variation of the method, the isolation comprises a filtration step. Multiple filtration steps, optionally one or more filtrations through a cleaning medium such as activated carbon or silica, for example Celite®, may also be provided.

[0057] During isolation as a solution or as a solid, the ease of separation of salts produced as by-products, especially magnesium salts and sodium and / or potassium salts, can be maximized, for example by filtration, optionally with a filter aid (e.g., Celite®) and / or centrifugation and / or decantation. This is because the aprotic polar solvent S A This can also be demonstrated by advantageously selecting the solvent. For example, when diethyl ether / dichloromethane in a ratio of about 1:1 (v / v) is used as the solvent, magnesium salts, potassium salts, and sodium salts, in particular, precipitate completely or nearly quantitatively, while the target compound iodotrimethylplatinum(IV) remains in solution. Thus, contamination of iodotrimethylplatinum(IV) with the resulting salt load is advantageously significantly reduced or prevented. The filtrate, centrifuged, or decanted material containing the platinum(IV) compound in solution can be stored and / or reacted in situ, i.e., without prior isolation and / or purification, with one or more further reactants.

[0058] Alternatively, iodotrimethylplatinum(IV) can be isolated as a solid, for example, by simple filtration, optionally using a filter aid such as Celite®, and / or by centrifugation and / or decantation, followed by removal of all volatile components such as the solvent and unreacted iodomethane. It is particularly advantageous that magnesium salts, particularly MgI and MgCl, and sodium and potassium salts, including, optionally, small amounts of unreacted suspended platinum(II) and / or platinum(IV) salts, can be easily and almost quantitatively, preferably quantitatively, removed by a filtration step and / or by centrifugation and / or decantation.

[0059] Isolation of iodotrimethylplatinum(IV) as a solution or solid may include further process steps such as, for example, "bulb-to-bulb" reduction of the mother liquor volume, i.e., reduction of the mother liquor concentration, addition and / or solvent exchange to precipitate the product from the mother liquor and / or to remove impurities and / or reactants, washing with, for example, dilute hydrochloric acid, water, and / or acetone, drying the product, etc. Each of the aforementioned steps may be provided in a different order and frequency.

[0060] Advantageously, the filtrate, centrifuged or decanted material can be subjected to further purification and / or isolation steps, which can be carried out quickly and uncomplicatedly and without special preparation efforts, in particular without ensuring an inert gas atmosphere. Overall, the purification and / or isolation of the target compound iodotrimethylplatinum(IV) is relatively simple and cost-effective.

[0061] Generally, the final product may still contain residues of solvent or salts precipitated as by-products. The iodotrimethylplatinum(IV) isolated as a solid has a purity of at least 97%, preferably greater than 97%, in particular greater than 98% or 99%. Even in the case of upscaling to industrial scale, reproducible yields are usually >90%, depending in particular on the choice of platinum compound(s), methyl Grignard compound, and solvent mixture.

[0062] This object also relates to the preparation of iodotrimethylplatinum(IV) obtained or obtainable by a method for producing iodotrimethylplatinum(IV) according to one of the above exemplary embodiments, and to the preparation of an ether S E and halogenated hydrocarbons S H aprotic polar solvent S containing A This can also be achieved by a solution comprising:

[0063] Aprotic polar solvent S A Also, two or more ethers S E and / or two or more halogenated hydrocarbons SH One embodiment of the solutions claimed herein may also be a solvent mixture containing at least one ether S E and at least one halogenated hydrocarbon S H The aprotic polar solvent S is miscible with A is at least one ether S E and at least one halogenated hydrocarbon S H In the context of the solutions claimed herein, two solvents are said to be miscible if they are miscible, i.e., do not exist as two phases, at least during each preparation and storage of the solutions claimed herein.

[0064] In the solution variants claimed herein, the aprotic polar solvent S A is chemically inert. The term "inert solvent" has already been defined above.

[0065] According to a further embodiment of the claimed solution, the aprotic polar solvent S A is the boiling point T A and the boiling point T A The boiling point T is between 30℃ and 140℃. A The temperature is preferably 31°C to 120°C, in particular 32°C to 110°C, or 33°C to 99°C. A can be quantitatively removed, for example, by simply applying negative pressure to the respective storage or reaction vessel and, optionally, by slightly increasing the temperature of the respective solution or the respective reaction mixture.

[0066] Iodotrimethylplatinum(IV) and aprotic polar solvents S A According to another embodiment of the solution comprising halogenated hydrocarbon S H is selected from the group consisting of alkyl halides and aromatic halogenated hydrocarbons. Advantageously, the halogenated hydrocarbon S H are chlorinated or brominated hydrocarbons. In particular, halogenated hydrocarbons S His selected from the group consisting of dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, dibromomethane, 1,1-dibromoethane, 1,2-dibromoethane, chlorobenzene, and isomers thereof, and mixtures thereof. Another embodiment of the claimed solution is an ether S E is selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, 1,4-dioxane, diethyl ether, methyl tert-butyl ether, di-n-propyl ether, diisopropyl ether, cyclopentyl methyl ether, and isomers thereof, and mixtures thereof. Advantageously, all of the aforementioned solvents are solvents commonly used in the chemical industry. Furthermore, the solvents have a boiling point of <140°C, in some cases <110°C, or <100°C. Quantitative removal of the solvent is therefore possible, for example, by simply applying negative pressure to the respective storage or reaction vessel, and optionally slightly increasing the temperature of the respective solution or the respective reaction mixture.

[0067] Iodotrimethylplatinum(IV) and aprotic polar solvents S AThe claimed solution, comprising: is particularly characterized by the fact that it can be produced in a simple, cost-effective, and reproducible manner by the above-described method. The solution has a very high purity, in particular being substantially free of impurities due to magnesium, sodium, and potassium salts, as well as elemental iodine. The above definitions apply to the terms "substantially free of impurities due to magnesium salts," "substantially free of impurities due to potassium salts," "substantially free of impurities due to sodium salts," and "substantially free of impurities due to elemental iodine." The yield of the compound iodotrimethylplatinum(IV) in the solution is good to very good. The formation of by-products, particularly elemental iodine, which are difficult to separate or cannot be separated at all, is advantageously reduced or completely avoided. Depending on the selected solvent mixture, the salt load, for example, produced in the form of NaCl, KCl, MgCl, or MgI, can be advantageously separated quantitatively or nearly quantitatively. Thus, the solution obtained or obtainable in this way and containing iodotrimethylplatinum(IV) and an aprotic polar solvent S A The purity of the solution containing meets the requirements described in the field of catalyst, pre-catalyst, and precursor production for chemical vapor deposition processes. In addition, the above method can also be carried out on an industrial scale, achieving comparable yields (including space-time yields) and purity.

[0068] Furthermore, the object is achieved by iodotrimethylplatinum(IV) obtained or obtainable according to the method for producing iodotrimethylplatinum(IV) according to one of the above exemplary embodiments.

[0069] In one embodiment of iodotrimethylplatinum(IV), the magnesium content is ≦500 ppm, advantageously ≦300 ppm. A further embodiment of iodotrimethylplatinum(IV) provides that the potassium content is ≦100 ppm, advantageously ≦50 ppm. A further variant of iodotrimethylplatinum(IV) provides that the sodium content is ≦100 ppm, advantageously ≦50 ppm. Furthermore, the iodotrimethylplatinum(IV) claimed herein, obtained or obtainable by a method according to one of the above exemplary embodiments, is present in particular as an off-white or white, optionally at least semi-crystalline powder, or in the form of off-white or white crystals.

[0070] The claimed iodotrimethylplatinum(IV) is particularly characterized by its simple, cost-effective, and reproducible preparation. Platinum(IV) compounds are obtained by the above-described method with very high purity, in particular substantially free of impurities from magnesium, potassium, or sodium salts and elemental iodine, in good to very good yields (including space-time yields). The formation of by-products that are difficult to separate or cannot be separated at all, especially elemental iodine, is advantageously reduced or completely avoided. Depending on the selected solvent mixture, the salt load, for example, in the form of NaCl, KCl, MgCl, or MgI, can be advantageously separated quantitatively or nearly quantitatively. Thus, the purity of the iodotrimethylplatinum(IV) obtained or obtainable in solid form meets the requirements set for reactants for producing catalysts, precatalysts, and precursors for chemical vapor deposition processes. Additionally, the above-described method can also be carried out on an industrial scale, achieving comparable yields (including space-time yields) and purities of the target compounds.

[0071] The above definitions apply to the terms "substantially free of impurities due to magnesium salts," "substantially free of impurities due to potassium salts," "substantially free of impurities due to sodium salts," and "substantially free of impurities due to elemental iodine."

[0072] Furthermore, the object is to prepare a compound containing iodotrimethylplatinum(IV) and ether S E and halogenated hydrocarbons S H aprotic polar solvent S containing A and iodotrimethylplatinum(IV), each of which has been obtained or can be obtained by a method for producing iodotrimethylplatinum(IV) according to one of the exemplary embodiments described above, as a reactant for producing a platinum(IV) compound.

[0073] The above use is Iodotrimethylplatinum(IV) and Ether S E and halogenated hydrocarbons S H aprotic polar solvent S containing A and using a solution containing or Using iodotrimethylplatinum(IV), A method for producing platinum(IV) compounds, wherein each platinum(IV) compound has been obtained or is obtainable by a method for producing iodotrimethylplatinum(IV) according to one of the exemplary embodiments described above; The method comprises: a) Iodotrimethylplatinum(IV) or iodotrimethylplatinum(IV) with aprotic polar solvent S A providing a solution comprising: b) synthesizing a platinum(IV) compound using iodotrimethylplatinum(IV) present in solution as a reactant.

[0074] The methods for producing platinum(IV) compounds described herein can be carried out as discontinuous processes or as continuous processes.

[0075] According to one embodiment of the method for producing platinum(IV) compounds claimed herein, a supply of iodotrimethylplatinum(IV), specifically iodotrimethylplatinum(IV), is prepared by dissolving iodotrimethylplatinum(IV) in an aprotic polar solvent, S Aand providing a solution comprising the compound in step a) comprises the in-situ production of iodotrimethylplatinum(IV) by a method for producing iodotrimethylplatinum(IV) according to one of the above-described embodiments. The expression "in-situ production" means that the reactants necessary for the synthesis of the compound thus produced are reacted in suitable stoichiometric amounts in a solvent or solvent mixture, and the resulting product is not isolated. Instead, the solution or suspension containing the compound produced in situ is generally reused directly, i.e., without isolation and / or further purification.

[0076] Aprotic polar solvent S A Also, two or more ethers S E and / or two or more halogenated hydrocarbons S H The presently claimed use of iodotrimethylplatinum(IV) or iodotrimethylplatinum(IV) and a polar aprotic solvent S A and an embodiment of the presently claimed use of a solution comprising iodotrimethylplatinum(IV) or an embodiment of the aforementioned solution for producing a platinum(IV) compound, further comprising at least one ether S E and at least one halogenated hydrocarbon S H The aprotic polar solvent S is miscible with A is at least one ether S E and at least one halogenated hydrocarbon S H In the context of the uses described herein or the methods claimed herein, two solvents are said to be miscible if they are miscible, i.e., do not exist as two phases, at least during each preparation and storage of the solutions claimed herein.

[0077] According to one embodiment of the presently claimed use or method, an aprotic polar solvent S Ais chemically inert. The term "inert solvent" has already been defined above.

[0078] In a further embodiment of the aforementioned use or method for producing a platinum(IV) compound, the aprotic polar solvent S A is the boiling point T A and the boiling point T A The boiling point T is between 30℃ and 140℃. A The temperature is preferably 31°C to 120°C, in particular 32°C to 110°C, or 33°C to 99°C. A can be quantitatively removed before and / or during and / or after the preparation of the respective platinum(IV) compound, for example, by simply applying negative pressure to the respective storage or reaction vessel and, optionally, by slightly increasing the temperature of the respective solution or the respective reaction mixture. In the simplest case, and optimally from an economical and ecological point of view, solvent S A acts as a solvent during the process for preparing the respective platinum(IV) compound or is at least a miscible component of the solvent used for this purpose.

[0079] According to another embodiment of the aforementioned use or method for producing a platinum(IV) compound, a halogenated hydrocarbon S H is selected from the group consisting of alkyl halides and aromatic halogenated hydrocarbons. Advantageously, the halogenated hydrocarbon S H are chlorinated or brominated hydrocarbons. In particular, halogenated hydrocarbons S H is selected from the group consisting of dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, dibromomethane, 1,1-dibromoethane, 1,2-dibromoethane, chlorobenzene, and isomers thereof, and mixtures thereof. Another embodiment of the aforementioned use or method for producing platinum(IV) compounds is the ether S Eis selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, 1,4-dioxane, diethyl ether, methyl tert-butyl ether, di-n-propyl ether, diisopropyl ether, cyclopentyl methyl ether, and isomers thereof, and mixtures thereof. Advantageously, all of the aforementioned solvents are solvents commonly used in the chemical industry. Furthermore, the solvents have a boiling point of <140°C, in some cases <110°C, or <100°C. Quantitative removal of the solvent before, during, and / or after the preparation of the respective platinum(IV) compound is therefore possible, for example, by simply applying negative pressure to the respective storage or reaction vessel, and optionally slightly increasing the temperature of the respective solution or the respective reaction mixture.

[0080] By using iodotrimethylplatinum(IV) as claimed herein, or with iodotrimethylplatinum(IV) as a solid or in a polar aprotic solvent S ABy the method described herein for preparing platinum(IV) compounds using iodotrimethylplatinum(IV) dissolved in iodotrimethylplatinum(IV) (each of which was obtained or can be obtained by the method for preparing iodotrimethylplatinum(IV) according to one of the above embodiments), multiple platinum(IV) compounds can be produced relatively inexpensively, easily, and quickly, with very high purity, and in good to very good yields. Examples of such platinum(IV) compounds are, in particular, (cyclopentadienyl)trimethylplatinum(IV) and its derivatives, such as (methylcyclopentadienyl)trimethylplatinum(IV), (ethylcyclopentadienyl)trimethylplatinum(IV), (iso-propylcyclopentadienyl)trimethylplatinum(IV), and (tert-butylcyclopentadienyl)trimethylplatinum(IV). Due to their very high purity, the platinum(IV) compounds obtainable or obtained in this manner are suitable for use as precursors in chemical vapor deposition processes for producing high-purity platinum layers or platinum-containing layers. Advantageously, the aforementioned platinum(IV) compounds can also be easily prepared on an industrial scale in very high purity and good to very good yields using iodotrimethylplatinum(IV) obtained or obtainable by the above-described method.

[0081] Furthermore, the object is achieved by a platinum(IV) compound obtained or obtainable according to a method for producing a platinum(IV) compound according to one of the above exemplary embodiments, which method comprises using iodotrimethylplatinum(IV) as a solid or by reacting iodotrimethylplatinum(IV) with an ether S E and halogenated hydrocarbons S H aprotic polar solvent S containing A and a solution comprising:

[0082] Platinum(IV) compounds thus obtained or obtainable are, for example, (cyclopentadienyl)trimethylplatinum(IV) and its derivatives, such as (methylcyclopentadienyl)trimethylplatinum(IV), (ethylcyclopentadienyl)trimethylplatinum(IV), (isopropylcyclopentadienyl)trimethylplatinum(IV), and (tert-butylcyclopentadienyl)trimethylplatinum(IV). The aforementioned platinum(IV) compounds and several further platinum(IV) compounds can be prepared by the addition of iodotrimethylplatinum(IV) as a solid or by the addition of iodotrimethylplatinum(IV) to an aprotic polar solvent S. A and (iii) a solution containing iodotrimethylplatinum(IV) and iodotrimethylplatinum(IV) ( ...

[0083] Furthermore, the purpose is to: Iodotrimethylplatinum(IV) and Ether S E and halogenated hydrocarbons S H aprotic polar solvent S containing A and by using a solution containing or This is achieved by using iodotrimethylplatinum(IV), Each of them has been obtained or can be obtained by a method for producing iodotrimethylplatinum(IV) according to one of the exemplary embodiments described above, in a chemical reaction, as a solution containing the catalyst or pre-catalyst, or as a catalyst or pre-catalyst.

[0084] The above use is Iodotrimethylplatinum(IV) and Ether S E and halogenated hydrocarbons S H aprotic polar solvent S containing A and using a solution containing or Using iodotrimethylplatinum(IV), A method for carrying out chemical reactions, each of which has been obtained or can be obtained by a method for producing iodotrimethylplatinum(IV) according to one of the exemplary embodiments described above, The method comprises: a) Iodotrimethylplatinum(IV) or iodotrimethylplatinum(IV) with aprotic polar solvent S A providing a solution comprising: b) carrying out a chemical reaction using iodotrimethylplatinum(IV) present as a solid or in solution as a catalyst or pre-catalyst.

[0085] The methods for carrying out the chemical reactions described herein can be carried out as discontinuous processes or as continuous processes.

[0086] According to one embodiment of the method claimed herein for carrying out a chemical reaction, according to one embodiment of the method for producing a platinum(IV) compound claimed herein, a supply of iodotrimethylplatinum(IV), in particular iodotrimethylplatinum(IV), and an aprotic polar solvent S Aand in step a) the provision of a solution comprising: and in situ production of iodotrimethylplatinum(IV) by a method for producing iodotrimethylplatinum(IV) according to one of the above-described embodiments, the expression "in situ production" having been defined above.

[0087] Aprotic polar solvent S A Also, two or more ethers S E and / or two or more halogenated hydrocarbons S H The presently claimed use of iodotrimethylplatinum(IV) or iodotrimethylplatinum(IV) and a polar aprotic solvent S A The embodiments of the presently claimed use of a solution comprising at least one ether S E and at least one halogenated hydrocarbon S H The aprotic polar solvent S is miscible with A is at least one ether S E and at least one halogenated hydrocarbon S H In the context of the uses described herein or the methods claimed herein, two solvents are said to be miscible if they are miscible, i.e., do not exist as two phases, at least during each preparation and storage of the solutions claimed herein.

[0088] According to one embodiment of the uses described herein or the methods claimed herein, an aprotic polar solvent S A is chemically inert. The term "inert solvent" has already been defined above.

[0089] In a further embodiment of the above-mentioned use or method for carrying out a chemical reaction, the aprotic polar solvent S A is the boiling point T A and the boiling point TA The boiling point T is between 30℃ and 140℃. A The temperature is preferably 31°C to 120°C, in particular 32°C to 110°C, or 33°C to 99°C. A can be quantitatively removed before and / or during and / or after carrying out a chemical reaction, for example, by simply applying negative pressure to the respective storage or reaction vessel and, optionally, by slightly increasing the temperature of the respective solution or the respective reaction mixture. In the simplest case, and optimally from an economical and ecological point of view, solvent S A functions as a solvent during a chemical reaction carried out in a platinum-catalyzed manner, or is at least a miscible component of a solvent used for this purpose.

[0090] According to another embodiment of the aforementioned use or method for carrying out a chemical reaction, a halogenated hydrocarbon S H is selected from the group consisting of alkyl halides and aromatic halogenated hydrocarbons. Advantageously, the halogenated hydrocarbon S H are chlorinated or brominated hydrocarbons. In particular, halogenated hydrocarbons S H is selected from the group consisting of dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, dibromomethane, 1,1-dibromoethane, 1,2-dibromoethane, chlorobenzene, and isomers thereof, and mixtures thereof. Another embodiment of a method for carrying out a chemical reaction is Eis selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, 1,4-dioxane, diethyl ether, methyl tert-butyl ether, di-n-propyl ether, diisopropyl ether, cyclopentyl methyl ether, and isomers thereof, and mixtures thereof. Advantageously, all of the aforementioned solvents are solvents commonly used in the chemical industry. Furthermore, the solvents have a boiling point of <140°C, in some cases <110°C, or <100°C. Quantitative removal of the solvent before, during, and / or after carrying out the chemical reaction is therefore possible, for example, by simply applying negative pressure to the respective storage or reaction vessel, and optionally slightly increasing the temperature of the respective solution or the respective reaction mixture.

[0091] According to one embodiment of the presently claimed use of iodotrimethylplatinum(IV) or one embodiment of a method for carrying out a chemical reaction using iodotrimethylplatinum(IV) as a catalyst or precatalyst, iodotrimethylplatinum(IV) is monomerized after providing iodotrimethylplatinum(IV) (see step a)). The term "monomerization" refers to providing monomeric, soluble, and catalytically active Me3PtI. Monomerization is typically achieved by thermal decomposition of iodotrimethylplatinum(IV), which typically exists as an oligomer, e.g., a dimer or tetramer.

[0092] In yet another embodiment of the presently claimed use or the presently claimed method for carrying out a chemical reaction using iodotrimethylplatinum(IV), the chemical reaction is an addition reaction to a carbon-carbon double bond and iodotrimethylplatinum(IV) is used as a pre-catalyst. In a further variation of the claimed use or a further variation of the claimed method, the addition reaction is a hydrosilylation of a carbon-carbon double bond.

[0093] In the presently claimed uses or the presently claimed methods for carrying out chemical reactions, iodotrimethylplatinum(IV) may be used as a solid or in a mixture of iodotrimethylplatinum(IV) and an aprotic polar solvent S A

[0023] The present invention can be used as a solution containing iodotrimethylplatinum(IV), each of which has been obtained or is obtainable by a method for producing iodotrimethylplatinum(IV) according to one of the above-described embodiments. Due to its very high purity, the iodotrimethylplatinum(IV) obtainable or obtained in this manner is suitable for use as a precatalyst or catalyst in several platinum-catalyzed reactions. In particular, iodotrimethylplatinum(IV) is substantially free of impurities due to magnesium salts, sodium salts, and potassium salts, as well as elemental iodine, as explained above. The above definitions apply to the terms "substantially free of impurities due to magnesium salts," "substantially free of impurities due to potassium salts," "substantially free of impurities due to sodium salts," and "substantially free of impurities due to elemental iodine." It is particularly advantageous that iodotrimethylplatinum(IV) can be prepared relatively cost-effectively, simply, and quickly by the above-described method in good to very good yields (including space-time yields), even on an industrial scale. The use of iodotrimethylplatinum(IV) claimed herein or the method described herein for carrying out a chemical reaction using iodotrimethylplatinum(IV), obtained or obtainable by a method for producing iodotrimethylplatinum(IV) according to one of the above embodiments, comprises at least a supply of iodotrimethylplatinum(IV) or a reaction of iodotrimethylplatinum(IV) with an aprotic polar solvent S A and (see step a)) can be easily, quickly and relatively cost-effectively carried out.

[0094] In addition, the object is achieved by the use of a platinum(IV) compound obtained or obtainable by a method for producing a platinum(IV) compound according to one of the above-described embodiments as a precursor compound for producing a platinum layer or a platinum-containing layer, in particular on at least one surface of a substrate.

[0095] The aforementioned use i. at least one platinum layer; or ii. at least one platinum-containing layer on at least one surface of a substrate using a platinum(IV) compound obtained or obtainable by a method for producing a platinum(IV) compound according to one of the above exemplary embodiments, The method comprises: a) providing a platinum(IV) compound; b) i. at least one platinum layer; or ii. at least one platinum-containing layer onto at least one surface of a substrate using a platinum(IV) compound as a precursor compound; Includes.

[0096] In step a), a supply of one or more platinum(IV) compounds may be provided. Furthermore, in step a), the one or more platinum(IV) compounds may be provided independently of one another as solids or as solutions containing one or more platinum(IV) compounds.

[0097] Here and below, we will not go into details about the exact stoichiometry of the platinum-containing layers or films that can be deposited, and the term "layer" is synonymous with the expression "film" and does not make any statement regarding the thickness of the layer or film.

[0098] Due to their very high purity, the platinum(IV) compounds used are particularly suitable as precursor compounds for producing high-quality platinum or platinum-containing layers on the surface of a substrate. This is particularly true for their production based on a method according to one of the above-described embodiments, i.e., using iodotrimethylplatinum(IV) obtained or obtainable by a method for producing iodotrimethylplatinum(IV) according to one of the above-described exemplary embodiments. This is because the iodotrimethylplatinum(IV) obtained or obtainable in this manner is substantially free of impurities due to magnesium salts, sodium salts, and potassium salts, as well as elemental iodine, which are detrimental to the coating process and therefore to the performance of the coated substrate. The above definitions apply to the terms "substantially free of impurities due to magnesium salts," "substantially free of impurities due to potassium salts," "substantially free of impurities due to sodium salts," and "substantially free of impurities due to elemental iodine." In addition, the platinum(IV) compound provided according to step a) can be prepared by the method for producing platinum(IV) compounds according to one of the above-described embodiments in a particularly simple and relatively cost-effective manner that facilitates its use on an industrial scale.

[0099] In one embodiment of the use described herein, or in one embodiment of the method described herein for producing a platinum layer or a platinum-containing layer on the surface of a substrate, the platinum(IV) compound provided in step a) is selected from the group consisting of (methylcyclopentadienyl)trimethylplatinum(IV), (ethylcyclopentadienyl)trimethylplatinum(IV), (iso-propylcyclopentadienyl)trimethylplatinum(IV), and (tert-butylcyclopentadienyl)trimethylplatinum(IV).

[0100] In another embodiment of the presently claimed use or the presently claimed method for producing a platinum or platinum-containing layer, the deposition of the platinum or platinum-containing layer in step b) is carried out by a vapor deposition process. In particular, the platinum or platinum-containing layer is deposited by an ALD process or an MOCVD process, in particular an MOVPE process.

[0101] The substrate may, for example, comprise or be made of one or more base metals. Alternatively or additionally, the substrate may comprise or be entirely made of one or more non-metallic materials. For example, corundum foil or a thin metal foil can be used as the substrate. The substrate itself may be part of a component. In one embodiment relating to the aforementioned use of a platinum(IV) compound as a precursor compound for producing a platinum layer or a platinum-containing layer, or in one embodiment relating to a method for producing a platinum layer or a platinum-containing layer on the surface of a substrate, the substrate is a wafer. The wafer may comprise silicon, silicon carbide, germanium, gallium arsenide, indium phosphide, glass such as SiO2, and / or plastic such as silicone, or may be entirely made of one or more such materials. The wafer may also have one or more wafer layers, each having a surface. The platinum layer or platinum-containing layer may be provided on the surface of one or more wafer layers.

[0102] Due to the very high purity of the platinum or platinum-containing layer, a substrate obtained or obtainable by the uses claimed herein or the methods described herein and comprising a platinum or platinum-containing layer can be particularly well used for the manufacture of electronic components, in particular electronic semiconductor components, or electrodes for fuel cells, in the latter case where the platinum or platinum-containing layer functions as a catalyst layer.

[0103] The objective is further to at least i. one platinum layer or ii. One platinum-containing layer on at least one surface thereof, The platinum layer or platinum-containing layer is produced using a platinum(IV) compound obtained or obtainable according to a method for producing a platinum(IV) compound according to one of the above exemplary embodiments.

[0104] The substrate may, for example, comprise or be made of one or more base metals. Alternatively or additionally, the substrate may comprise or be entirely made of one or more non-metallic materials. For example, corundum foil or a thin metal foil may be used as the substrate. The substrate itself may be part of a component. In one embodiment, the substrate is a wafer. The wafer may comprise silicon, silicon carbide, germanium, gallium arsenide, indium phosphide, glass such as SiO2, and / or plastic such as silicone, or may be entirely made of one or more such materials. The wafer may also have one or more wafer layers, each having one surface. In this case, one or more surfaces may have a platinum layer or a platinum-containing layer.

[0105] The very high purity of the at least one platinum or platinum-containing layer on at least one surface of the substrate claimed herein makes it particularly suitable for producing electronic components, in particular electronic semiconductor components, or electrodes for fuel cells, in which case the at least one platinum or platinum-containing layer functions as a catalyst layer.

[0106] The object is also achieved by a method for producing an electronic component, in particular an electronic semiconductor component, or an electrode for a fuel cell, using a platinum(IV) compound obtained or obtainable by a method for producing a platinum(IV) compound according to one of the above exemplary embodiments, the method comprising: a) providing a platinum(IV) compound; b) i. at least one platinum layer; or ii. at least one platinum-containing layer onto at least one surface of a substrate; c) completing an electronic component, in particular an electronic semiconductor component, or an electrode for a fuel cell.

[0107] In step a), a supply of one or more platinum(IV) compounds may be provided. Furthermore, in step a), the one or more platinum(IV) compounds may be provided independently of one another as solids or as solutions containing one or more platinum(IV) compounds.

[0108] The substrate may, for example, comprise or be made of one or more base metals. Alternatively or additionally, the substrate may comprise or be entirely made of one or more non-metallic materials. For example, corundum foil or a thin metal foil may be used as the substrate. The substrate itself may be part of a component. In one embodiment, the substrate is a wafer. The wafer may comprise silicon, silicon carbide, germanium, gallium arsenide, indium phosphide, glass such as SiO2, and / or plastic such as silicone, or may be entirely made of one or more such materials. The wafer may also have one or more wafer layers, each having one surface. In this case, one or more platinum layers or one or more platinum-containing layers may be deposited on one or more surfaces of the wafer.

[0109] Due to their very high purity, the platinum(IV) compounds used herein are particularly suitable as precursor compounds for the production of electronic semiconductor components and electrodes for fuel cells. This is particularly true for their production based on a method according to one of the above-described embodiments, i.e., using iodotrimethylplatinum(IV) obtained or obtainable by a method for producing iodotrimethylplatinum(IV) according to one of the above-described exemplary embodiments. This is because the iodotrimethylplatinum(IV) obtained or obtainable in this manner is substantially free of impurities due to magnesium salts, sodium salts, and potassium salts, as well as elemental iodine, which are detrimental to the coating process and therefore to the performance of the coated substrate. The above definitions apply to the terms "substantially free of impurities due to magnesium salts," "substantially free of impurities due to potassium salts," "substantially free of impurities due to sodium salts," and "substantially free of impurities due to elemental iodine." In addition, the platinum(IV) compound provided according to step a) can be prepared by the method for producing platinum(IV) compounds according to one of the above-described embodiments in a particularly simple and relatively cost-effective manner that facilitates its use on an industrial scale.

[0110] According to one of the above-described embodiments, a platinum(IV) compound is provided using iodotrimethylplatinum(IV) obtained or obtainable by the method for producing iodotrimethylplatinum(IV). Iodotrimethylplatinum(IV) can be prepared by the claimed method in a simple, cost-effective, and reproducible manner with very high purity and good to very good yields (including space-time yields). In addition, the claimed method is characterized by its ability to be carried out on an industrial scale with comparable yields (including space-time yields) and purity of the target compound. Overall, the claimed method for producing iodotrimethylplatinum(IV) and the iodotrimethylplatinum(IV) thus prepared are considered satisfactory from an ecological and economical point of view. Due to its very high purity, the iodotrimethylplatinum(IV) obtained or obtainable in this way is particularly suitable as a reactant for producing high-purity platinum(IV) precursor compounds, which serve to deposit platinum or platinum-containing layers, as well as a precatalyst and catalyst. Due to the very high purity of the platinum layer or platinum-containing layer, the substrates obtained or obtainable using the platinum(IV) precursor compounds described above can be particularly well used for the production of electronic components, in particular electronic semiconductor components, and electrodes for fuel cells.

[0111] Other features, details and advantages of the invention can be gleaned from the claims and from the following description of the examples.

[0112] Description of a procedure for the synthesis of iodotrimethylplatinum(IV) Materials and Methods: All reactions, including subsequent filtration, were carried out under standard inert gas conditions. Solvents and reagents used were purified and dried by standard procedures. For Grignard reagents used as solutions, the content was determined by titration. The platinum, magnesium, and potassium contents of the isolated product, iodotrimethylplatinum(IV), were measured by ICP-OES.

[0113] Example 1: Preparation of Me3PtI starting from K2[PtCl6], MeI, and MeMgI in CH2Cl2 125 g of K2[PtCl6] (50.4 g of Pt, 0.258 mol) was transferred to a 1 L reaction vessel and 500 mL of CHCl2 was added. Then, 80 mL (1.29 mol, 5 equiv.) of iodomethane was added at room temperature. At a flow temperature of 2 °C, 430 mL of a solution of MeMgI in diethyl ether (3 M, 1.29 mol, 5 equiv.) was added within 45 min. After the addition was complete, the suspension was stirred at a flow temperature of 10 °C for 16–20 h. The color of the suspension slowly changed from yellow to beige. Gas production was observed during the reaction, and a temperature increase of up to 5 °C relative to the flow temperature was observed. The excess Grignard reagent was quenched by adding 50 mL of acetone within 20 min. The suspension was filtered at room temperature, and the filter cake was washed with 2000 mL of CHCl2. The solvent of the combined filtrates was removed using a rotary evaporator (end conditions: 40°C, <500 mbar). 500 mL of acetone was then added and the pressure was slowly reduced to 300 mbar. 500 mL of degassed distilled water was then added and the pressure was slowly reduced to <100 mbar. The product suspension was then filtered. The product obtained as a solid was washed with dilute hydrochloric acid, water (until the pH was neutral) and finally with acetone. 93 g of iodotrimethylplatinum(IV) (53.1% Pt) was isolated in the form of an off-white powder (metal yield 98%). The elution of 53.1% Pt in benzene-d6 was carried out using a rotary evaporator. 1 H-NMR shows the product signals: 195 It showed only a singlet at 1.74 ppm with a Pt satellite, H-PT coupling = 77.21 Hz. The magnesium content was <300 ppm. The potassium content was <50 ppm.

[0114] Example 2: Preparation of Me3PtI starting from K2[PtCl6], MeI, and MeMgI in CH2Cl2 This was carried out similarly to that described in Example 1. The only difference was that the addition of the 3 molar ethereal MeMgI solution was carried out at a stream temperature of 20°C instead of 2°C, and after the addition was complete the suspension was also stirred for 16-20 hours at a stream temperature of 20°C. Iodotrimethylplatinum(IV) was obtained in similar yields and quality.

[0115] The invention is not limited to one of the above-described embodiments, but can instead be modified in many ways.

[0116] It can be seen that the present invention relates to a method for producing iodotrimethylplatinum(IV), and iodotrimethylplatinum(IV) obtainable or obtained by said method, and its use as a reactant, precatalyst, and catalyst for producing high-purity platinum(IV) compounds. The subject of the present invention is also the aforementioned platinum(IV) compounds and their use as precursors for depositing platinum and platinum-containing layers on the surface of a substrate. The present invention also relates to a substrate comprising a platinum or platinum-containing layer on one surface, and a method for producing electronic components, in particular electronic semiconductor components, or electrodes for fuel cells, using a platinum(IV) compound obtained or obtainable using iodotrimethylplatinum(IV) obtainable by the method described herein.

[0117] According to one of the above-described embodiments, a platinum(IV) compound is provided using iodotrimethylplatinum(IV) obtained or obtainable by the method for producing iodotrimethylplatinum(IV). Iodotrimethylplatinum(IV) can be prepared by the claimed method in a simple, cost-effective, and reproducible manner with very high purity and good to very good yields (including space-time yields). Furthermore, the methods described herein can also be carried out on an industrial scale with comparable yields (including space-time yields) and purity of the target compound. Overall, the claimed method for producing iodotrimethylplatinum(IV) and the iodotrimethylplatinum(IV) thus prepared are considered satisfactory from an ecological and economical point of view. Due to its very high purity, the iodotrimethylplatinum(IV) thus obtained or obtainable is particularly suitable for use as a reactant, precatalyst, and catalyst for producing high-purity platinum(IV) precursor compounds useful for depositing platinum or platinum-containing layers.

[0118] All features and advantages emerging from the claims and the description, for example from structural details, spatial arrangements, and method steps, may be relevant to the present invention, either alone or in various combinations.

Claims

1. 1. A method for producing iodotrimethylplatinum(IV), comprising: Ether S Ｅ and halogenated hydrocarbons S Ｈ aprotic polar solvent S containing Ａ Among them, at least one platinum compound selected from the group consisting of M 2 [PtX 6 ] and PtX 4 (wherein M is selected from alkali metals and X represents Cl, Br, or I); at least one methyl Grignard compound according to the general formula MeMgX, where Me represents a methyl group and X is independently selected from the group consisting of Cl, Br, and I; including reaction with iodomethane, The ether S Ｅ is selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, 1,4-dioxane, diethyl ether, methyl tert-butyl ether, di-n-propyl ether, diisopropyl ether, cyclopentyl methyl ether, and isomers thereof, and mixtures thereof; the halogenated hydrocarbon SH is selected from chlorinated alkyls; The method wherein the molar ratio of Pt metal:MeMgX:iodomethane is from 1:4:4 to 1:6:

6.

2. 2. The method of claim 1, wherein the MeMgX is MeMgI.

3. The aprotic polar solvent S Ａ is the boiling point T Ａ and the boiling point T Ａ The method according to claim 1 or 2, wherein the temperature is 30°C to 140°C.

4. 4. The method of claim 1, wherein the molar ratio of MeMgX:iodomethane is from 1:1.5 to 1.5:

1.

5. The reaction comprises the following steps: i) providing at least one platinum compound; ii) adding the iodomethane; iii) adding at least one methyl Grignard compound according to the general formula MeMgX; The method according to any one of claims 1 to 4, comprising:

6. The method according to any one of claims 1 to 5, wherein the reaction is carried out in an inert gas atmosphere.

7. After the reaction, iodotrimethylplatinum(IV) Iodotrimethylplatinum (IV) and the aprotic polar solvent S Ａ or as a solution containing The method of any one of claims 1 to 6, wherein the step comprising isolating is carried out as a solid.