LOW PRESSURE PROCESS FOR SYNTHESIS OF Pt(PF3)4 INVOLVING A SOLUBLE INTERMEDIATE AND STORAGE OF OBTAINED Pt(PF3)4

Abstract

To provide a method for synthesizing Pt(PF3)4 used as a precursor for a film-forming composition.SOLUTION: A method for synthesizing Pt(PF3)4 comprises: forming a suspension in a solvent of a platinum precursor Pt(Hal)2 (wherein Hal=F, Cl, Br, or I) and metal powder; introducing an excess amount of PF3 into the suspension of Pt(Hal)2 and the metal powder; forming a soluble reaction intermediate Pt(Hal)2(PF3)x in the solvent through a reaction between PF3 and Pt(Hal)2 (wherein Hal=F, Cl, Br, or I; x=1, 2) under a reaction condition; and forming Pt(PF3)4 through a reaction between Pt(Hal)2(PF3)x, the metal powder, and the excess amount of PF3 in the solvent.SELECTED DRAWING: Figure 2a

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority under 35 U.S.C. §119(a) and (b) to U.S. patent application Ser. No. 17 / 546,169, filed December 9, 2021, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to the synthesis and storage of Pt(PF3)4, which is used as a precursor for film-forming compositions. Pt(PF3)4 is Pt(Hal)2 (Hal = F, Cl, Br, or I) or Pt(Hal)2(PF3) x (Hal = F, Cl, Br or I; x = 1, 2), metal powder and PF3 at low pressure in an anhydrous solvent capable of dissolving the reaction intermediate Pt(Hal)2(PF3), where Pt(Hal)2(PF3) x can be formed from Pt(Hal)2 and PF3. The resulting Pt(PF3)4 is then stored at room temperature under air- and moisture-free conditions in devices and ampoules made of metal, such as stainless steel, preferably with passivated or electropolished interior surfaces. [Background technology]

[0003] Chemical vapor deposition (CVD) and atomic layer deposition (ALD) methods have attracted considerable interest in the fabrication of catalysts and batteries on an industrial scale. Precursors suitable for high-throughput industrial processes ideally have high vapor pressures at room temperature, ensuring maximum application rates in the shortest time and at temperatures that do not compromise precursor stability. Platinum is widely used as a catalyst, and a wide variety of materials containing platinum on supports are now available. Nevertheless, processes utilizing the deposition of platinum from the gas phase are rare due to the lack of suitable platinum precursors.

[0004] For example, platinum hexafluoride (PtF6, CAS number 13693-05-5), which is solid at room temperature but volatile at room temperature, is rarely applied as a deposition precursor due to its very strong oxidizing and correspondingly strong etching properties. (MeCp)PtMe3 (CAS number 94442-22-5), which is widely cited for deposition processes, has a vapor pressure of 1 Torr at 69 °C but begins to slowly decompose at 50 °C (Journal of Vacuum Science & Technology, B: Microelectronics and Nanometer Structures (1990), 8(6), 1826-9), preventing the use of this compound in high-throughput processes.

[0005] The complex Pt(PF3)4 (CAS No. 19529-53-4) is a volatile liquid at room temperature and has a vapor pressure of 36 Torr at room temperature (RD Sanner et al., Report (1989), (UCRL-53937; Order No. DE90000902)), making it a nearly ideal potential precursor for Pt deposition from the gas phase. However, this compound has very limited commercial availability. The reason for the lack of scalability may be the technical difficulties associated with the synthesis of Pt(PF3)4, a nearly ideal potential precursor for Pt deposition from the gas phase. However, this compound has very limited commercial availability (only one supplier in Japan [Japan (Gram quantities from Advanced Chemicals) and no suitable ALD process using this chemistry has been reported to date. The reason for the lack of scalability may be the technical difficulties associated with synthesizing Pt(PF3)4 in gram quantities, and the even greater difficulty in industrially scalable forms with acceptable yields and realistic operating conditions. do.

[0006] The original synthesis of Pt(PF3)4, which was achieved in gram quantities and yields of 70-80%, was carried out by reaction (1) at 100-150 atm. PF3 and 100°C, applying "fine and oxide-free copper powder" (Angew. Chem. Int. Ed. 1965, 4, 521). The synthesis procedure is described in a single sentence in the literature and in a later reference that employs the same method, without any details regarding the reaction and the equipment. The reaction requires the application of PF3 gas under high pressure to a mixture of two solids (PtCl2 and Cu powder), making it highly unscalable even for a skilled chemist. PtCl2 + 2Cu + PF3 (excess) → Pt(PF3)4 + 2CuCl (1)

[0007] It is noteworthy that the reaction of PtCl2 with PF3 (2) at 60-80 °C and undisclosed pressure afforded Pt(PF3)4 in only 1% yield (Inorg. Nucl. Chem. Letters, Vol. 4, pp. 275-278, 1968). Such low yields make this approach unfeasible for industrial implementation. PtCl2 + PF3 (excess) → Pt(PF3)4 + other products (2)

[0008] Flow reactions (3) from the same starting compounds under undisclosed pressures produced only donor-acceptor adducts (Inorg. Nucl. Chem. Letters, Vol. 4, pp. 275-278, 1968). 3PtCl2 + PF3 (excess) → PtCl2(PF3)2 + [PtCl2(PF3)]2(3)

[0009] The compounds PtCl(PF) and [PtCl(PF)] were synthesized from solid PtCl and PF gas (J. Chatt, AA Williams, J. Chem. Soc. [London] 1951, 3061). According to a passage on page 200 of Zeitschrift fur Anorganische und Allgemeine Chemie, Band 364, 1969, pp. 192-208, the solid compound can react with PF to form Pt(PF) under undisclosed "higher" pressures. This "higher pressure" can be assumed to be 40-150 atm, since this is the range reported for the synthesis of Pt(PF) in Zeitschrift fur Anorganische und Allgemeine Chemie, Band 364, 1969, pp. 192-208. The compound PtCl2(PF3)2 is soluble in the polar solvent CDCl3, and its NMR was reported in J. Chem. Res., Syn., 1981, 2, 38. According to J. Chem. Soc. [London] 1951, 3061, the solubility of PtCl2(PF3)2 in benzene is reported to be "low," with molar concentrations ranging from 0.005 to 0.01 M, and the melting point of PtCl2(PF3)2 is 118.3°C. The FTIR spectrum of PtCl2(PF3)2 is disclosed in Journal of Chemical Research, Synopses (1981), (2), 37.

[0010] Alternatively, the preparation of Pt(PF3)4 has been achieved in gram quantities in a difficult-to-obtain rotary autoclave under a 40 atm PF3 atmosphere in 95% yield by reaction (4) (Zeitschrift fur Anorganische und Allgemeine Chemie. Band 364. 1969, 192-208): PtCl4 + 4Cu + 4PF3 → Pt(PF3)4 + 4CuCl(4)

[0011] PtCl4+6PF3→Pt(PF3)4+2PF3Cl2(5) Reaction (5) without copper produces PF3Cl2, but Pt is preferred due to its similar volatility. It should be noted that the purification of (PF3)4 is complex (Zeitschrift fur Anorganische und Allgemeine Chemie. Band 364. 1969, pp. 192-208). The addition of copper reduces the amount of PF3Cl2, suggesting that reactions (4) and (5) may result in Pt(PF3)4 containing impurities that do not meet the quality standards for CVD and ALD precursors. Notably, reaction (4) also requires mixing two solids and contacting them with PF3 gas, compounding the scalability issues already mentioned. The reaction of PtCl4 with excess PF3 further renders scalability impractical.

[0012] Russian Patent No. 2478576C2 discloses a two-step process under a PF3 (6a and 6b) atmosphere at 2-6.3 MPa (19.7-62.2 atm), in which CuO is reduced in the same autoclave, after which K2PtCl6 and PF3 are introduced. CuO + H2 → Cu + H2O(6a) K2PtCl6 + 4Cu + PF3 (excess) → Pt(PF3)4 + 4CuCl + 2KCl (6b)

[0013] Russian Patent No. 2201463C1, U.S. Patent No. 7044995B2, Terekhov et al. (Terekhov et al., International Symposium on Recycling of Metals and Engineered Materials, Proceedings, October 4, 2000, pp. 487-491), and Kovtun et al. (Publications of the Australasian Institute of Mining and Metallurgy (2002), 2 / 2002, pp. 367-372) disclose the extraction of platinum from ore by the interaction of "PGM matte" or "feedstock" with PF3 gas, resulting in the formation of volatile Pt(PF3). The feedstock was hypothesized to contain Pt metal and interact with PF3 via (7d). However, as first reported in 1891, Pt and PF3 give the platinum compound F5PPt (H. Moissan, Bull. Soc. Chim. France). 5,454 (1891)), this compound was thought to be similar to (PCl3)PtCl2. 3Pt+4HNO3+18HCl→3H2PtCl6+4NO+8H2O(7a) H2PtCl6+2NH3→(NH4)2PtCl6(7b) (NH4)2PtCl6+H2=2NH4Cl+4HCl+Pt (under ultrasound irradiation) (7c) Pt + PF3 (excess amount) → Pt(PF3)4 (7d)

[0014] In addition, according to Chem. Ber. 101, 138-142 (1968), Pt metal does not react with PF3 under any conditions. U.S. Patent No. 7,044,995 B2 discloses that finely dispersed Pt metal (platinum black, particle size <20 μm) does not react with PF3, and only "activated" Pt metal obtained by applying the multi-step method (7a-7c) and reduction with hydrogen under ultrasonic irradiation in step (7c) can react with PF3.

[0015] The solvent effect can be negative for reactions initiated from PtCl2, since, according to Zhurnal Neorganicheskoi Khimii (1970), 15(9), 2445-8, in contrast to the solvent-free reaction of PtCl2 + I2 = PtCl2I2, the reaction of these reagents in organic solvents gave various products but not PtCl2I2. A number of classes of solvents react with PF3, PtCl2 and reduced Pt species and therefore cannot be used for the synthesis of Pt(PF3)4. These The class of solvents includes primary amines, which react with PF3 to give RNHPF2, (RNH)2PF2H, and (RNH)2PF (see J. Chem. Soc. A (1970), (11), 1935-8). Tertiary amines, such as NMe3 and NEt3, form adducts with PF3 (see Inorganic Chemistry (1963), 2, 384-8). Alcohols and PF3 form organic phosphites (see Transactions of the Illinois State Academy of Science (1936), 29 (No. 2), 89-91). The general pattern of reactivity of P(Hal)3 (Hal = Cl, Br) toward alcohols has been widely reported. Dienes, olefins, unsaturated aldehydes, and ketones react with PF3 to form adducts, as shown for PCl3 and PBr3 (see Uspekhi Khimii (1968), 37(5), 745-77). Acetone reacts with PF3 and Pt(II) compounds (see Zhurnal Obshchei Khimii (1975), 45(3), 512-18; Inorganica Chimica Acta (1997), 264(1-2), 297-303). Halocarbons can react with Pt compounds under reaction conditions via oxidative addition, as shown in selected examples in [Organometallics (2019), 38(10), 2273; Organometallics 2009, 28, 1358-1368; and Organometallics (1987), 6(12), 2548], where the oxidative addition of alkyl and aryl halides to platinum complexes is a widely reported reaction.

[0016] In conclusion, existing synthetic approaches to Pt(PF3)4 are highly dependent on reaction conditions. Changing these conditions can significantly reduce the yield of Pt(PF3)4 or result in different products, demonstrating a lack of process robustness. Furthermore, no synthetic processes have been reported to date that require PF3 pressures lower than 3 MPa (29.6 atm, 420 psig), as claimed in Russian Patent No. 2478576C2. Most syntheses require specialized equipment or conditions, such as high-pressure autoclaves, that are not typically available for large-scale process scaling. In particular, existing methods lack technical details, and the purity of Pt(PF3)4 is not reported in any of the literature. Furthermore, all of the disclosed methods are essentially dry approaches, which also poses significant challenges for industrial scale-up.

[0017] Numerical standards exist for the catalytic conversion of hydrocarbons by platinum compounds, such as Journal of the American Chemical Society (2002), 124(42), 12550-12556. Jackson et al., J. Am. Chem. Soc. 1997, 119, 7567-7572, demonstrated the catalytic activity of Pt compounds for the model system Pt(PF) - saturated and aromatic cyclic hydrocarbons. Small platinum clusters generated from Pt(PF) reacted with various saturated and aromatic cyclic hydrocarbons (cyclohexane, benzene, toluene). Jackson et al. clarified the catalytic and dehydrogenation behavior of platinum. Therefore, it can be assumed that introducing a hydrocarbon solvent into the reaction system and then heating it may result in a mixture of products due to various catalytic reactions, and this may be considered undesirable for the selective synthesis of Pt(PF) . For these reasons, Pt(PF3)4 has never been synthesized and manipulated in organic solvents, and only anhydrous HF and SO2 have been applied as solvents to study Pt(PF3)4 chemistry (Drews et al., Chem. Eur. J. 2008, 14, 4280-4286).

[0018] To date, the potentially ideal Pt(PF3)4 precursor has not been applied solely due to the lack of scalable methods, and therefore, providing a scalable method for the production of Pt(PF3)4 in high yields would be a major advance. Summary of the Invention [Means for solving the problem]

[0019] 1. A method for synthesizing Pt(PF3)4 (CAS number 19529-53-4): General formula Pt(Hal)2(PF3) x The platinum compound having the formula Pt(Hal)2(PF3) was dissolved in anhydrous solvent. x forming a solution (wherein Hal=F, Cl, Br or I, x=1, 2); Metal powder and excess PF3 were mixed with Pt(Hal)2(PF3) x adding to the solution; and Pt(Hal)2(PF3) under reaction conditions x A method is disclosed that includes forming Pt(PF) via a reaction of PF and a metal powder. The method of the present disclosure may include one or more of the following aspects: Reaction conditions including a reaction temperature in the range of approximately -120 to 200°C; Reaction conditions including a reaction temperature in the range of approximately 30-200°C; Reaction conditions including a reaction temperature ranging from room temperature to approximately 180°C; Reaction conditions including a reaction temperature ranging from room temperature to approximately 130°C; · reaction conditions including a reaction temperature in the range of approximately 80-130°C; Reaction conditions including reaction pressures ranging from approximately 10 psig to approximately 3000 psig; Reaction conditions including reaction pressures ranging from approximately 20 psig to approximately 1000 psig; Reaction conditions including reaction pressures ranging from approximately 20 to approximately 300 psig; Reaction conditions including a reaction pressure of less than approximately 300 psig; Anhydrous solvents with a boiling point above 150°C; · Anhydrous solvents with a boiling point above 200 ° C; Metal powders, such as copper, zinc or aluminum powders; · Metal powder, which is copper powder; Metal powder, which is zinc powder; · Metal powder, which is aluminum powder; Metal powders with lower electrode potential than Pt; metal powders that do not interact with PF3 and do not form complexes with PF3 under the reaction conditions; Metal powder with an appropriate particle size range that allows it to maintain its powder form during the reaction process; Metal powders with particle sizes ranging from 200 to 900 microns; Metal powders with particle sizes in the range of 300-500 microns; ·Platinum compound Pt(Hal)2(PF3) x (Hal=F, Cl, Br or I; x=1, 2), dispersing a platinum precursor having the general formula Pt(Hal)2 in an anhydrous solvent to form a suspension of Pt(Hal)2 (wherein Hal = F, Cl, Br, or I); introducing PF3 into a suspension of Pt(Hal)2; The reaction of PF3 and Pt(Hal)2 produces the platinum compound Pt(Hal)2(PF3) x forming a solution of (Hal=F, Cl, Br, or I; x=1, 2) in an anhydrous solvent; further comprising the steps of: · Anhydrous platinum precursor Pt(Hal)2; ·PtCl2, the platinum precursor Pt(Hal)2; ·Platinum precursor Pt(Hal)2, which is anhydrous PtCl2; Anhydrous platinum compound Pt(Hal)2(PF3) x (Hal = F, Cl, Br or I, x = 1, 2); ·PtCl2(PF3)2, the platinum compound Pt(Hal)2(PF3) x (Hal = F, Cl, Br or I, x = 1, 2); ·Pt(Hal)2(PF3), anhydrous PtCl2(PF3)2, is the platinum compound x (Ha l=F, Cl, Br or I, x=1, 2); ·moreover: purifying Pt(PF3)4 under air- and moisture-free conditions in a metal trap; and Storing the purified Pt(PF3)4 in a metal container under air- and moisture-free conditions. Here, the steps to save are removing moisture from the interior surface of the container; and Electropolishing the interior surface of the container; or Passivating the container with PF3 before introducing purified Pt(PF3)4 Contains; a metal for the trap selected from carbon steel, stainless steel, or stainless steel alloy 316, respectively; a metal for the container selected from carbon steel, stainless steel, or stainless steel alloy 316, respectively; · Anhydrous solvents, which are hydrocarbon solvents; ·General formula (C n H 2n+1 )2O(n≧1) and H3C(O(CH2)2) n a hydrocarbon solvent selected from oxyhydrocarbon solvents having OCH3 (n≧1); ·General formula (C n H 2n+1 ) x C6H 6-x a hydrocarbon solvent selected from arene solvents having (x≧1, n≧1); ·General formula C n H 2n+2 a hydrocarbon solvent selected from alkane solvents having (n≧1); anhydrous solvents, which are dry alkane solvents selected from decane, di-, tri-, tetra-, penta- and hexadecane, etc.; Anhydrous solvents, which are dry arene solvents selected from xylene, mesitylene, cymene, pentylbenzene, diisopropylbenzene, diisobutylbenzene, etc.; Anhydrous solvents, which are dry ether solvents selected from dibutyl ether, dihexyl ether, dioctyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, etc.; Anhydrous solvents, which are arene solvents selected from xylene, mesitylene, cymene, pentylbenzene, diisopropylbenzene, diisobutylbenzene, etc.; dry ether solvents, preferably dibutyl ether, dihexyl ether, dioctyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; Dry arene solvents, preferably xylene, mesitylene, cymene, pentylbenzene, diisopropylbenzene, diisobutylbenzene; dry alkane solvents, which are preferably mixtures of alkanes such as di-, tri-, tetra-, penta- and hexadecane, as well as those known as mineral oil; Anhydrous solvents capable of dissolving the reaction intermediates; Pt(Hal)2(PF3) x anhydrous solvent capable of dissolving (Hal=F, Cl, Br or I, x=1, 2); ·Anhydrous solvent capable of dissolving PtCl2(PF3)2); ·Anhydrous solvent that does not react with Pt(PF3)4; Anhydrous solvents that do not react with Pt(Hal)2 (Hal = F, Cl, Br or I); ·Anhydrous solvent that does not react with PtCl2; Xylene is an anhydrous solvent; Hexadecane is an anhydrous solvent; Pt(PF3)4 yields in the range of approximately 70-99.9%; Pt(PF3)4 yields in the range of approximately 70-95%; · Pt(PF3)4 yields in the range of approximately 70-93%; Purity of Pt(PF3)4 >99% by weight; Purity of Pt(PF3)4 greater than 99.5% by weight; Purity of Pt(PF3)4 of approximately 90-99.9 wt%; Purity of Pt(PF3)4 of approximately 99.0-99.9% by weight; a purity of Pt(PF3)4 of approximately 99.5 to 99.9% by weight; and · Formed Pt(PF3)4 with scalability to large industrial scale.

[0020] Also disclosed is a method for producing and storing Pt(PF3)4 (CAS number 19529-53-4), which comprises: a) forming a suspension of a platinum precursor Pt(Hal)2 (where Hal = F, Cl, Br or I) and metal powder in an anhydrous solvent; b) introducing an excess of PF3 into a suspension of Pt(Hal)2 and metal powders; c) The reaction of PF3 and Pt(Hal)2 (where Hal = F, Cl, Br, or I; x = 1, 2) under low pressure conditions to give the reaction intermediate Pt(Hal)2(PF3) soluble in anhydrous solvents. x forming a d) Pt(Hal)2(PF3) in anhydrous solvent x , reacting metal powder and PF to form Pt(PF) ; e) purifying Pt(PF3)4 under air- and moisture-free conditions in a metal trap; and f) storing the purified Pt(PF3)4 in a metal container under air- and moisture-free conditions. The method of the present disclosure may include one or more of the following aspects: ·PtCl2, the platinum precursor Pt(Hal)2; Anhydrous solvents with a boiling point above 150°C; · Anhydrous solvents with a boiling point above 200 ° C; ·General formula (C n H 2n+1 )2O(n≧1) and H3C(O(CH2)2) n Oxyhydrocarbon solvents having the general formula (C n H 2n+1 ) x C6H 6-x(x≧1, n≧1) or an arene solvent having the general formula C n H 2n+2 an anhydrous solvent which is a hydrocarbon solvent selected from alkane solvents having (n≧1); Anhydrous solvents such as xylene or hexadecane; Anhydrous solvents capable of dissolving reaction intermediates; Pt(Hal)2(PF3) x (Hal=F, Cl, Br or I, x=1, 2) anhydrous solvent capable of dissolving ·Anhydrous solvent capable of dissolving PtCl2(PF3)2); ·Anhydrous solvent that does not react with Pt(PF3)4; Anhydrous solvents that do not react with Pt(Hal)2 (Hal = F, Cl, Br or I); ·Anhydrous solvent that does not react with PtCl2; Reaction temperatures in the range of approximately 30-200°C; Reaction temperatures in the range of approximately 80-130°C; Low pressure conditions, which are pressures below approximately 300 psig; Low pressure conditions, with pressures in the range of approximately 20 to 300 psig; Metal powders, such as copper, zinc or aluminum powders; · Metal powder, which is copper powder; Metal powders with lower electrode potential than Pt; metal powders that do not interact with PF3 and do not form complexes with PF3 under the reaction conditions; Metal powder with an appropriate particle size range that allows it to maintain its powder form during the reaction process; Metal powders with particle sizes ranging from 200 to 900 microns; Metal powders with particle sizes in the range of 300-500 microns; Pt(PF3)4 yields in the range of approximately 70-99.9%; Pt(PF3)4 yields in the range of approximately 70-95%; · Pt(PF3)4 yields in the range of approximately 70-93%; - Purity of Pt(PF3)4, approximately 90-99.9 wt% after purification; · Purity of Pt(PF3)4 after purification is 99.0-99.9 wt%; a metal for the trap and a metal for the container, each selected from carbon steel, stainless steel, or stainless steel alloy 316; and ·moreover: Electropolishing the interior surface of the container; or Passivating the container with PF3 before introducing purified Pt(PF3)4 The steps include:

[0021] Also disclosed is a method for producing and storing Pt(PF3)4 (CAS number 19529-53-4), which comprises: a) forming a suspension of a platinum precursor, Pt(Cl)2, in an anhydrous solvent selected from xylene or hexadecane; b) Introducing an excess of PF3 into a suspension of Pt(Cl)2 to form Pt(Cl)2(PF3) by reaction of PF3 and Pt(Cl)2. x forming a solution of (x=1, 2) in an anhydrous solvent; c) Copper powder in Pt(Cl)2(PF3) x (x=1, 2) to a solution; d) Copper powder, PF3 and Pt(Cl)2(PF3) x to form Pt(PF3)4 in an anhydrous solvent at a reaction temperature ranging from 30 to 200°C and a low PF3 pressure ranging from 20 to 300 psig; e) purifying Pt(PF) under air- and moisture-free conditions in a stainless steel trap; and f) storing the purified Pt(PF3)4 under air- and moisture-free conditions in a stainless steel container, the interior surface of which is electropolished or passivated with PF3. The disclosed method may include one or more of the following aspects: Copper powder with a particle size ranging from 200 to 900 microns; and Copper powder with particle size ranging from 300 to 500 microns.

[0022] Notation and Nomenclature In the following detailed description and claims, numerous abbreviations, symbols, and terms that are generally well known in the art are used. While a definition is typically provided at the first occurrence of each acronym, such as stainless steel (SS), certain abbreviations, symbols, and terms are used throughout the following specification and claims, including the following:

[0023] In the following detailed description and claims, numerous abbreviations, symbols and terms that are generally well known in the art are used.

[0024] As used herein, the indefinite article "a" or "an" means one or more.

[0025] As used herein, "about" or "around" or "approximately" in the text or claims means ±10% of the stated value.

[0026] As used herein, "room temperature" in the text and claims means approximately 18°C ​​to approximately 25°C.

[0027] As used herein, "atmospheric pressure" in the text or claims means This means approximately 1 atm.

[0028] Standard abbreviations for elements from the periodic table are used herein. It should be understood that elements can be referred to by these abbreviations (e.g., Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, H refers to hydrogen, and Hal refers to halogens, which are F, Cl, Br, and I).

[0029] Unique CAS Registry Numbers (i.e., "CAS") assigned by the Chemical Abstract Service are provided to identify the particular molecules disclosed.

[0030] As used herein, the term "hydrocarbon" refers to saturated or unsaturated functional groups containing only carbon and hydrogen atoms.

[0031] As used herein, the terms "low pressure," "low reaction pressure," or "low PF3 pressure" refer to pressures below 300 psig or below 20 atm. The same applies to "reduced pressure," which refers to pressures reduced or lowered to below 300 psig or 20 atm. In some cases, "low pressure," "low reaction pressure," or "low PF3 pressure" can refer to a pressure range ranging from 20 psig to 300 psig.

[0032] Ranges may be expressed herein as from one about a particular value and / or to another about a particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and / or to the other particular value, including all combinations within said ranges. Any and all ranges described herein include their endpoints (i.e., x=1 to 4 or x ranges from 1 to 4 includes x=1, x=4, and x=any number therebetween), regardless of whether the term "inclusive" is used.

[0033] As used herein, references to "one embodiment" or "embodiment" mean that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of the invention. The appearances of the phrase "in one embodiment" in various places throughout this specification do not necessarily all refer to the same embodiment, nor do separate or alternative embodiments necessarily mean that they are mutually exclusive. The same applies to the term "implementation."

[0034] As used in this application, the word "exemplary" is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete manner.

[0035] Additionally, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless otherwise specified or clear from the context, "X employs A or B" is intended to mean any of the natural inclusive permutations. That is, "X employs A or B" is satisfied if X employs A; if X employs B; or if X employs both A and B. Additionally, as used in this application and the appended claims, the articles "a" and "an" should be construed generally to mean "one or more" unless otherwise specified or clear from the context that the singular form is intended.

[0036] The foregoing and various other aspects, features, and advantages of the present invention, as well as the invention itself, may be more fully understood by reference to the following detailed description of the invention when considered in conjunction with the following drawings, which are presented for purposes of illustration only and are not intended to limit the invention. [Brief explanation of the drawings]

[0037] [Figure 1] FIG. 1 is a block diagram of an exemplary disclosed system for synthesizing Pt(PF3)4. [Figure 2a] FIG. 2a is a flow chart of an exemplary disclosed process for the synthesis of Pt(PF) starting from Pt(Hal) (Hal = F, Cl, Br, or I). [Figure 2b]FIG. 2b is a flow chart of an exemplary disclosed process for the synthesis of Pt(PF) starting from Pt(Hal)(PF) (x=1, 2; Hal=F, Cl, Br, or I). [Figure 3] Figure 3 shows the 19F NMR spectra of the PtCl2(PF3)2 crystals and the supernatant solution in hexadecane from the reaction mixture stopped at the PtCl2(PF3)2 stage. [Figure 4] FIG. 4 is a graph of the Pt(PF3)4 assay and relative amounts of impurities over time in electropolished stainless steel small canisters at room temperature. DETAILED DESCRIPTION OF THE INVENTION

[0038] Methods for synthesizing, preparing, producing, and storing Pt(PF3)4 (CAS No. 19529-53-4) are disclosed. The disclosed methods are scalable for producing Pt(PF3)4 in high yields, and the produced Pt(PF3)4 can be used as a precursor for Pt-containing film deposition in microelectronic devices or the catalytic industry.

[0039] The disclosed synthesis method involves the synthesis of an insoluble platinum compound, Pt(Hal)2 (Hal = F, Cl, Br, or I), and a soluble reaction intermediate, the platinum compound Pt(Hal)2(PF3). x (Hal = F, Cl, Br, or I; x = 1, 2), which involves the formation of a soluble reaction intermediate from an insoluble Pt(Hal) (Hal = F, Cl, Br, or I) suspension under low pressure conditions, and the reaction of the soluble intermediate with a metal powder and a co-reactant such as PF to form Pt(PF).

[0040] Alternatively, the soluble intermediate Pt(Hal)2(PF3) x (Hal = F, Cl, Br, or I; x = 1, 2) can be isolated and purified, so the disclosed synthesis method can produce soluble Pt(Hal)2(PF3) under certain reaction conditions. xIt can be a one-step wet synthesis of Pt(PF3)4 using (Hal = F, Cl, Br, or I; x = 1, 2) reacted with a metal powder and a co-reactant such as PF3 to form Pt(PF3)4. Preferably, Hal = Cl. Preferably, the metal powder is copper powder.

[0041] Furthermore, a robust, high-yielding, and scalable synthesis of Pt(PF3)4 is disclosed that can proceed at low pressure and can be carried out in conventional reactors or equipment. More specifically, Pt(PF3)4 can be prepared from Pt(Hal)2 (Hal = F, Cl, Br, or I) or Pt(Hal)2(PF3). x The platinum compound may be synthesized from a platinum compound selected from the group consisting of (Hal = F, Cl, Br, or I; x = 1, 2) in an anhydrous solvent under low PF3 pressure with PF3 and a metal powder, such as copper powder. The metal powder may have a particle size ranging from approximately 200 to 900 microns, preferably approximately 300 to 500 microns. The anhydrous solvent may be used to prepare the reaction intermediate Pt(Hal)2(PF3). x (Hal = F, Cl, Br or I; x = 1, 2), where Pt(Hal)2(PF3) x (Hal = F, Cl, Br, or I; x = 1, 2) can be formed from Pt(Hal)2 and PF3 under certain reaction conditions, such as low pressure conditions. In this specification, the platinum compound Pt(Hal)2(PF3) x (Hal = F, Cl, Br, or I; x = 1, 2) can be isolated and purified for use as a reactant or starting material for the synthesis of Pt(PF3)4. The yield of Pt(PF3)4 using the disclosed synthesis method can range from approximately 70 to 99.9%. The present disclosure also includes a purification process for the product Pt(PF3)4 using a metal trap and storage conditions for the purified Pt(PF3)4 in a container. Pt(PF3)4 can be stored under air- and moisture-free conditions in devices and ampoules made of stainless steel, preferably with passivated or electropolished inner surfaces. Pt(PF3)4 can be stored at room temperature in metal containers, such as stainless steel containers and stainless steel containers with passivated or electropolished inner surfaces, without changing its purity.

[0042] As mentioned above, the lack of scalable methods in the art may be due to the fact that commonly available reactors for pilot plant synthesis and large-scale production are not designed for operation under high pressure and for efficient agitation (mixing) of air-sensitive solids. That is, commercially available reactors (e.g., manufactured by High Pressure Equipment Company) capable of operating under high pressures of approximately 100 atm lack the necessary agitation for the reaction to proceed. Additionally, commercially available reactors (e.g., manufactured by Buchiglas USA) have difficulty even achieving the dry ice temperature required to condense PF3 within the reactor. While agitation of the solids can be improved to some extent using specially designed agitator shafts, this does not address parasitic reactions such as PtCl2 / Cu, which result in platinum metal and reduce the yield of Pt(PF3)4. Additionally, removal of impurities is difficult, necessitating additional purification steps that are expensive and uncertain.

[0043] The disclosed method for the robust, high-yield, and scalable synthesis of Pt(PF3)4 can proceed under low PF3 pressures, e.g., less than 20 atm, and can be carried out in commonly used, commercially available reactors. A potentially ideal Pt(PF3)4 precursor has not been applied until now solely due to the lack of a scalable synthetic method. Therefore, the disclosed method, which provides a method capable of leading to the scaled-scale production of Pt(PF3)4 in high yields, represents a significant advance in the art. The lack of a scalable synthetic method is due to the fact that commonly used commercial reactors for pilot plant synthesis and bulk production, as discussed above, are not designed for operation under high pressures (e.g., greater than 30 atm) and are not designed for efficient agitation (mixing) of air-sensitive solids.

[0044] The disclosed method may demonstrate, for the first time, that the reaction aimed at synthesizing Pt(PF) from PtCl + PF + Cu in a solvent proceeds via the fully soluble intermediate PtCl(PF) under reaction conditions (e.g., low pressures of 20-300 psig and temperatures of 80-130°C) when the starting material Pt(Hal) (Hal = F, Cl, Br, or I) is PtCl and the metal powder is Cu powder. It is generally accepted that the solubility of inorganic compounds such as PtCl(PF) is lower in saturated hydrocarbon solvents than in the arene solvent benzene. Therefore, relying on solubility in the hydrocarbon solvent hexadecane is counterintuitive, and relying on such low solubility in an arene solvent is also counterintuitive.

[0045] According to the prior art, Pt(PF3)4 was typically prepared from PtCl2, K2PtCl6, and K2PtCl6, while K2PtCl6 is required to reduce the PF3 pressure. Both PtCl2 and K2PtCl6 are insoluble in the disclosed solvents (e.g., arenes, saturated hydrocarbons). As shown in the following examples and comparative examples, the solvent effect is significant for platinum starting compounds, such as PtCl2 (Example 1, Table 1, Comparative Example 1), and for K2PtCl6. The same is not true for KPtCl (Example 7, Table 5). While the addition of a disclosed solvent (e.g., xylene, hexadecane) is beneficial for reactions initiated from PtCl, the solvent-free reaction from the starting compound KPtCl: K2PtCl6 + Cu (excess) + PF3 (excess) → Pt(PF3)4 + 4CuCl + 2KCl The yield of Pt(PF3)4 was higher in hexadecane solvent than in the reaction starting from K2PtCl6, indicating that the solvent benefit is beneficial for certain Pt precursors such as PtCl2, PtF2, PtI2, PtBr2, etc. Therefore, the use of solvents in the synthesis of Pt(PF3)4 from Pt(Hal)2 (Hal = F, Cl, Br, or I) is novel.

[0046] FIG. 1 is a block diagram of an exemplary disclosed solid-gas PtCl2 + PF3 + Cu system for the synthesis of Pt(PF3)4. As shown, a metal powder, such as Cu powder 11, is first added to reactor 16 via line 101. In the disclosed process, an anhydrous solvent is used as solvent 14. The solvent applied as solvent 14 may have a moisture content of 0 to 50 ppm, preferably 0 to 10 ppm, and more preferably 0 to 1 ppm. Solvent 14 may be dried by contacting it with a desiccant selected from 3 Å or 4 Å molecular sieves or activated alumina through drying process 104. Drying process 104 can be performed at a temperature range of 10 to 50°C, preferably at room temperature, for a period of 0.5 to 20 hours. In some embodiments, drying process 104 can be achieved by holding the solvent in container 15 with the molecular sieves or by passing it through a column containing a desiccant (not shown) in drying process 104. The moisture content in container 15 after drying can be measured by Karl Fischer titration or any other suitable analysis. Solvent 14 can be a commercially available solvent and can be degassed by applying a vacuum-inert gas cycle or by bubbling an inert gas containing less than 0.5 ppm O and moisture before contact with the desiccant. The solvent or anhydrous solvent 14 can be stored in container 15 or sent to reactor 16 via line 105 immediately after drying process 104. Container 15 containing dried anhydrous solvent 14 can be stored before the next step or can be transported to another location where reactor 16 is located.

[0047] Thereafter, PtCl2 12 is charged into reactor 16 under an inert atmosphere (e.g., nitrogen, argon, helium) by any suitable means, such as the application of a solid addition funnel 102. The PtCl2 12 can be anhydrous PtCl2. Hereinafter, PF3 13 is charged into reactor 16 via addition line 103 by pressure differential. Reactor 16 may be pre-evacuated and heated, or at room temperature and pre-evacuated, or contain PF3 at a constant pressure and temperature. Prior to the addition of PF3, reactor 16 may be depressurized to 0.1 to 50 Torr, preferably 0.1 to 2 Torr, to remove an inert gas selected from nitrogen, argon, and helium. The absence of non-condensable gases (nitrogen, argon, and helium) in reactor 16 makes distillation of the product Pt(PF3)4 more efficient. Alternatively, the PF3 added to reactor 16 may contain 1 atm of nitrogen, argon, or helium at room temperature. Adding PF313 to reactor 16 creates a PF3 pressure of 20 psig to 300 psig in reactor 16. PF3 can be added in portions during the process or continuously. The amount of PF3 pressure depends on the pressure rating of the reactor used, and PF3 can be added in portions or continuously during the process and recycled after the process.

[0048] The reactor 16 may be a typical vessel having stirring, temperature and pressure control, and reaction monitoring means for use in the synthesis and purification of Pt(PF3)4. The reactor 16 may be operated at a temperature ranging from about -120°C to about 200°C, preferably from room temperature to 180°C, more preferably from room temperature to 130°C, and at a pressure ranging from about 10 psig to about 3000 psig, preferably from about 2 The reactor 16 has cooling and heating equipment to maintain a corresponding pressure of 0 psig to approximately 1000 psig, more preferably from about 20 psig to about 300 psig. The reactor 16 is connected to an empty vessel to act as ballast and has a vent to vent the reactor contents if overpressurized. The reactor 16 is connected to nitrogen and vacuum lines (not shown) and a PF3 scrubber (not shown), as well as to traps 18 and 20 to recover the product Pt(PF3)4 via line 107 and recycle unreacted PF3 via line 110.

[0049] Solvent 14 may include various organic solvents. In some embodiments, solvent 14 may be a dry alkane solvent selected from decane, di-, tri-, tetra-, penta-, or hexadecane. In this case, Cu powder 11, anhydrous PtCl2 12, and dry alkane solvent 14 are charged into reactor 16 to form a suspension. The starting amount of PtCl2 solids in solvent 14 is 1% to 50%, preferably 5% to 40%, and more preferably 20% to 30%. The molar ratio of PtCl2 12 to Cu powder 11 is 1:2 to 1:20, preferably 1:6 to 1:10. That is, the molar ratio of Pt to Cu is 1:2 to 1:20, preferably 1:6 to 1:10. Reactor 16 is evacuated to 0.1 to 50 Torr, preferably 0.2 to 5 Torr, before introducing PF313.

[0050] Alternatively, solvent 14 can be a dry arene solvent selected from xylene, mesitylene, cymene, pentylbenzene, diisopropylbenzene, or diisobutylbenzene. In this case, Cu powder 11, anhydrous PtCl2 12, and dry arene solvent 14 are charged into reactor 16. The starting amount of PtCl2 solids in the solvent is 1% to 50%, preferably 10 to 40%, and more preferably 20 to 30%. The molar ratio of PtCl2 to Cu is 1:2 to 1:20, preferably 1:6 to 1:10. That is, the molar ratio of Pt to Cu is 1:2 to 1:20, preferably 1:6 to 1:10. Reactor 16 is evacuated to 0.1 to 50 Torr, preferably 0.2 to 5 Torr, prior to the introduction of PF3 13.

[0051] Alternatively, the solvent 14 can be a dry ether solvent selected from dibutyl ether, dihexyl ether, dioctyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. In this case, Cu powder 11, anhydrous PtCl2 12, and dry ether solvent 14 are charged into a reactor 16. The starting amount of PtCl2 solids in the solvent is 1% to 50%, preferably 10 to 40%, and more preferably 20 to 30%. The molar ratio of PtCl2 to Cu is 1:2 to 1:20, preferably 1:6 to 1:10. That is, the molar ratio of Pt to Cu is 1:2 to 1:20, preferably 1:6 to 1:10. The reactor 16 is depressurized to 0.1 to 50 Torr, preferably 0.2 to 5 Torr, before the introduction of PF313.

[0052] After PF313 is introduced into the reactor 16, the reaction mixture is initially a suspension of PtCl212 and Cu powder 11 in the solvent 14 under PF313 pressure. Then, the reactor 16 is heated while stirring the reaction mixture, thereby forming a PtCl2(PF3) x (x=1, 2) is formed. The reaction can be stopped after heating for 20-80 minutes with stirring in the preferred temperature range described above, and PtCl2(PF3)2 can be isolated from the solvent, reaction by-products, residual PF3, etc. The compound PtCl2(PF3) x (x=1, 2) are soluble in solvent 14, which can be evidenced by NMR spectroscopy, as shown in Figure 3. The reaction continues under PF3 pressure in reactor 16, where PF3 and PtCl2 (PF3) x (x=1, 2) is dissolved in a solvent and reacted with copper powder 11. During the course of the reaction, PF313 is consumed. PF313 can be added to reactor 16 in portions or can be added continuously to maintain a constant selected pressure. Once all starting and intermediate platinum compounds have been consumed, the pressure in reactor 16 remains constant at a given temperature.

[0053] The reaction time may be in the range of 1 hour to 24 hours, preferably 4 hours to 8 hours. The conversion rate may be monitored by the consumption rate of PF3 and the pressure change in the reactor 16 by in situ Raman spectroscopy or any other suitable technique.

[0054] In some embodiments, the reaction in reactor 16 occurs in hexadecane under 20-50 psig of PF3 at a temperature of 100-125° C. and is completed in 6 hours. Alternatively, in some embodiments, the reaction in reactor 16 occurs in xylene under 20-40 psig of PF3 at a temperature of 100-125° C. and is completed in 5 hours.

[0055] After the reaction is complete, the reaction mixture is cooled to 20-65°C, preferably 30-45°C. The remaining gas consisting of PF3, Pt(PF3)4, and solvent is sent to pre-evacuated trap 17, which is maintained at a temperature ranging from -196°C to -160°C. PF3 (melting point -151.5°C, boiling point -101.9°C), Pt(PF3)4 (melting point -15°C), and solvent are condensed in pre-evacuated trap 17. After condensation of Pt(PF3)4 in pre-evacuated trap 17 is complete, depressurization is intermittently applied to remove residual gases such as nitrogen, argon, and helium, creating a reduced pressure in the range of 0.1-50 Torr, preferably 0.2-2 Torr, to facilitate distillation of the remaining Pt(PF3)4 from reactor 16 in pre-evacuated trap 17. Before condensing the reaction product containing Pt(PF3)4 and PF3, the pre-depressurized trap 17, Pt(PF3)4 trap 18 and PF3 trap 20 are pre-depressurized to 0.01 to 10 Torr, preferably 0.1 to 1 Torr.

[0056] Alternatively, after the reaction is completed, the reaction mixture is cooled to 20 to 65°C, preferably 30 to 45°C, and a portion of the gas containing PF3, Pt(PF3)4, and the solvent is sent to pre-pressurized trap 17 through line 106, which is maintained at a temperature in the range of -60 to -80°C. PF3 is not condensed, and Pt(PF3)4 and the solvent are condensed in pre-pressurized trap 17. After the Pt(PF3)4 and the solvent are condensed in pre-pressurized trap 17, the uncondensed PF3 is sent from pre-pressurized trap 17 by a pressure difference to PF3 trap 20, which is maintained at a temperature in the range of -160 to -196°C. Then, another portion of the gas containing PF3, Pt(PF3)4, and the solvent is sent from reactor 16 to pre-pressurized trap 17. This cycle continues until all of the PF3 is condensed in PF3 trap 20 and all of the Pt(PF3)4 is condensed in pre-pressurized trap 17.

[0057] Preferably, condensation of the gaseous product is performed by the steps described above for a continuous process because, even with efficient engineering and cooling of the pre-depressurized trap 17 with dry ice-isopropanol (-79°C), the continuous flow of gas from reactor 16 results in 20-60% of the Pt(PF3)4 in PF3 trap 20 being bypassed 108, necessitating an additional step (not shown) to recover all of the Pt(PF3)4 from PF3 trap 20. The additional step may include warming trap 20 to a temperature above the boiling point of PF3 (-102°C), typically -79°C (dry ice cooling), and capturing all of the PF3 in a first separate trap (not shown) cooled with liquid nitrogen. After capturing all of the PF3, trap 20 is warmed to room temperature, and the Pt(PF3)4 is captured in a second separate trap (not shown). The PF3 trapped in the first individual trap can be recycled to PF3 13 through line 110 for synthesis in reactor 16. The pre-depressurized trap 17, the Pt(PF3)4 trap 18 and the PF3 trap 20 and all connecting lines are made of metal or are made of metal, where the metallic material is Preferably, the materials are carbon steel, stainless steel, and stainless steel alloys. In some embodiments, the pre-evacuated trap 17, the Pt(PF3)4 trap 18, and the PF3 trap 20 and all connecting lines are made of stainless steel. All traps may have passivated or electropolished inner surfaces.

[0058] Pt(PF3)4 is separated from PF3 by fractional distillation under air- and moisture-free conditions. After collecting the volatile species, the pre-evacuated trap 17 is warmed to a temperature in the range of -20 to -90°C, preferably -60 to -80°C, and PF3 is distilled in PF3 trap 20, which is maintained at a temperature in the range of -160 to -196°C. The PF3 in PF3 trap 20 can be stored, transferred to a different location, or recycled as PF3 13 for subsequent synthesis.

[0059] Pt(PF3)4, contaminated with reaction by-products such as solvent and solid copper chloride, remains in the pre-evacuated trap 17 after PF3 consumption. The Pt(PF3)4 in the pre-evacuated trap 17 has a purity of 90-99% and contains 0.1-5% PF3, 0.1-10% solvent, and 0.1-1% other impurities, preferably phosphorus oxofluoride and solid copper chloride. The Pt(PF3)4, solvent, and solids are separated when the mixture is maintained at a temperature in the range of 10-40°C, preferably room temperature, and the receiver is maintained at a temperature in the range of -50 to -196°C. The apparatus and receiver can be pre-evacuated before distillation, and the pressure during distillation is 0.01 to 760 Torr, preferably 0.1 to 5 Torr. More specifically, the Pt(PF3)4 recovered in the pre-evacuated trap 17 is purified by distillation in the Pt(PF3)4 trap 18. In one embodiment, the pre-evacuated trap 17 containing Pt(PF3)4 after PF3 consumption is warmed to 0-40°C, preferably room temperature, and Pt(PF3)4 is distilled from the pre-evacuated trap 17 at a pressure of 0.01-50 Torr, preferably 0.1-2 Torr, while the Pt(PF3)4 trap 18 is maintained at a temperature in the range of -15 to -196°C.

[0060] The Pt(PF3)4 recovered in the Pt(PF3)4 trap 18 has a purity of 70 to 99.9% w / w, preferably 80 to 99.9% w / w, more preferably 90 to 99.9% w / w, even more preferably 95 to 99.9% w / w, and even more preferably 99.0 to 99.99% w / w after purification. Preferably, the recovered Pt(PF3)4 has a purity of 99.50 to 99.99% w / w, and contains 0 to 0.5% PF3, 0.01 to 0.5% other impurities (such as phosphorus oxofluorides and thermal decomposition products of Pt4(PF3)8), and 0 to 0.5% residual solvent. The purity of Pt(PF3)4 is 1 H, 19 F, 31 P, 195 Pt NMR, FTIR, and Raman spectroscopy were used.

[0061] The purified Pt(PF3)4 may have approximately 0% to approximately 0.1% by weight of PF3 impurities, preferably approximately 0% to approximately 0.05% by weight of PF3 impurities. The purified Pt(PF3)4 may have approximately 0% to approximately 1% by weight, preferably approximately 0% to approximately 0.05% by weight of phosphofluorides and oxofluorides including PF3, POF3, (HO)POF2, and (HO)2POF. The purified Pt(PF3)4 may have 0% to approximately 0.1% by weight, preferably approximately 0% to approximately 0.05% by weight of platinum compounds other than Pt(PF3)4. Pt(Hal)2, Pt4(PF3)8, and Pt(Hal)2(PF3) in Pt(PF3)4. x The total concentration of (Hal = F, Cl, Br, or I, x = 1, 2) after purification can be about 0 wt.% to about 0.1 wt.%, preferably about 0 wt.% to about 0.05 wt.%. Furthermore, the purified Pt(PF3)4 can have 0.1 ppmw to 1000 ppmw of the solvent used in the synthesis, preferably about 0 ppmw to 200 ppmw of the solvent, more preferably 0 ppmw to 50 ppmw of the solvent, and even more preferably 0 ppmw to 20 ppmw of the solvent. Furthermore, the purified Pt(PF3)4 may have approximately 0 ppmw to approximately 100 ppmw of hydrogen fluoride and 0 ppmw to approximately 50 ppmw of hydrogen chloride. In addition, the purified Pt(PF3)4 may have approximately 0 ppb to 10 ppm of trace metals such as iron, nickel, manganese, cobalt, copper, etc. The remaining PF3 is recycled for the synthesis of Pt(PF3)4.

[0062] In some embodiments, an internal standard such as MeSi can be used to measure the amount of organic compounds in Pt(PF). In some embodiments, sample preparation can include adsorption of the organic solvent with a suitable adsorbent, such as C8-derivatized silica gel.

[0063] In some embodiments, Pt(PF) trap 18 may include two subsequent traps, such as trap 18a and trap 18b (not shown), for distillation to obtain Pt(PF) of a desired purity. After purification, Pt(PF) may be stored in Pt(PF) trap 18 before packaging into metal ampule 19 for shipping, vapor deposition, or storage. Alternatively, Pt(PF) may be stored in metal ampule 19 after packaging 109. Metal ampule 19 may be a metallic container / vessel made from metals such as stainless steel, carbon steel, and stainless steel 316 alloy. The inner surface of metal ampule 19 may be passivated with PF or electropolished.

[0064] Moisture derived from the surfaces of the metal Pt(PF3)4 trap 18 and the metal ampoule 19 can be removed by heating Pt(PF3)4 at approximately 100 to 170°C under reduced pressure before introducing it into the metal Pt(PF3)4 trap 18 and the metal ampoule 19. Alternatively, moisture derived from the surfaces of the metal Pt(PF3)4 trap 18 and the metal ampoule 19 can be removed by passivating the trap container with PF3 before introducing Pt(PF3)4 into the metal Pt(PF3)4 trap 18 and the metal ampoule 19.

[0065] The purified Pt(PF3)4 can be stored in a metal Pt(PF3)4 trap 18 or a metal ampoule 19 at a temperature ranging from -80 to 60°C, preferably from 10 to 40°C, and more preferably from 20 to 25°C. The disclosed method includes storing Pt(PF3)4 in a metal container, such as a stainless steel, carbon steel, or stainless steel 316 alloy container. The inner surface of the metal container can be passivated with PF3 or electropolished. The stainless steel container can be a small, open-ended stainless steel sample cylinder or a small, electropolished stainless steel canister. In an exemplary embodiment, purified Pt(PF3)4 was stored in a small, open-ended stainless steel sample cylinder at room temperature for two months without any change in Pt(PF3)4 purity. Alternatively, purified Pt(PF3)4 was stored in a small, electropolished stainless steel canister at room temperature for two months without any change in Pt(PF3)4 purity.

[0066] The disclosed method involves the production of a soluble intermediate, Pt(Hal)2(PF3), shown in Figure 2a. x (x=1, 2; Hal=F, Cl, Br, or I), which can be represented by a so-called solid-gas Pt(Hal)2-M-PF3 synthesis process in solution. Here, Hal is F, Cl, Br, or I, preferably Hal is Cl; M is a metal (e.g., Cu), and the Pt(Hal)2-M-PF3 synthesis process then becomes a PtCl2-Cu-PF3 synthesis process. The method of the present disclosure produces Pt(PF3)4 in high yield (i.e., 70-99.9%) and high purity (i.e., greater than 99%, preferably greater than 99.99%), and also enables the storage and delivery of high-purity Pt(PF3)4 without loss of purity. The use of a hydrocarbon solvent is advantageous for the disclosed solid-gas PtCl2-Cu-PF3 reaction process, where the solvent acts to dissolve the reaction intermediates (e.g., fluorine) formed from the insoluble starting materials, solid platinum compound PtCl2 and PF3 gas, under appropriate reaction conditions. For example, a solvent capable of dissolving the platinum complex PtCl2(PF3)2) while not reacting with Pt(PF3)4 can be used. The use of such a solvent makes it possible to obtain Pt(PF3)4 in high yield, in a shorter time, and at low PF3 pressure. The low PF3 pressure in the disclosed Pt(PF3)4 synthesis method eliminates the need for reactor cooling to condense PF3, allowing the use of a reactor with a low pressure rating. As a result, commonly available equipment and reactors can be utilized in the disclosed Pt(PF3)4 synthesis method. This results in a Pt(PF3)4 synthesis process that is scalable to large-scale industrial scales and requires limited equipment complexity due to the low pressure requirement. Here, reaction conditions include reaction temperature, reaction pressure, etc.

[0067] In the disclosed synthesis method, the problems of low, moderate, and irreproducible yields in solid-gas reactions and the high pressure of PF3 required for the synthesis of Pt(PF)4 are solved by adding the disclosed solvent to the PtCl2-Cu-PF3 reaction system. The addition of the solvent achieves the synthesis of Pt(PF3)4 under low PF3 pressure in a shorter time with reproducible high yields (Table 1, Examples 1-4). The reason for the improved synthesis process is the solubility of PtCl2(PF3)2, which is obtained in situ from PtCl2 and PF3 under low-pressure reaction conditions. It is generally known that solution-solid reactions are much more efficient than reactions between two different solids and gases. The addition of a solvent transforms the solid-gas PtCl2-Cu-PF3 reaction system into a much more efficient solution-solid reaction. Although the use of solvents in synthesis is common practice, it is not an obvious solution for a given reaction system and can even be subject to objections due to the reaction conditions applied, the high reactivity of PF3, and the diverse platinum coordination and catalytic chemistry in organic solvents.

[0068] The addition of a solvent to the solid-gas Pt(Hal)2-M-PF3 synthesis system overcomes the problems of low, moderate, and irreproducible yields in solid-gas reactions (see Comparative Example 1 below) and the high PF3 pressures (50–150 Atm) required for the synthesis of Pt(PF3)4. The addition of a solvent enables the synthesis of Pt(PF3)4 under low PF3 pressures in a shorter time and with reproducible high yields (see Examples 2–4 below). The reason for the improved yield is the solubility of the reaction intermediate PtCl2(PF3)2, which is obtained in situ from PtCl2 and PF3 under certain reaction conditions (Figure 3). Again, solution-solid reactions are known to be significantly more efficient than reactions between two different solids and gases. In the following Examples 2 to 4, the addition of a solvent to the PtCl-Cu-PF synthesis system enabled the synthesis of Pt(PF) at a PF pressure of 10 to 50 psig in 5 to 6 hours with a reproducible high yield (see also Example 1). This is because the solid-gas PtCl-Cu-PF synthesis system became a solution-solid reaction. As a result, commonly available equipment and reactors can be used in the disclosed Pt(PF) synthesis process.

[0069] A suitable solvent should be "inert" to the starting compounds, intermediates, and product Pt(PF3)4 and should not react with the starting compounds, intermediates, and product Pt(PF3)4 under the reaction conditions. In other words, a suitable solvent should not be catalytically converted by the starting compounds, intermediates, and product Pt(PF3)4 under the reaction conditions, and the solvent should not convert the starting compounds and products to other compounds. A suitable solvent should dissolve only at least one intermediate in the reaction to achieve a solution-solid reaction that is fairly efficient, reproducible, and therefore more scalable than a reaction between two different solids and a gas. A suitable solvent should be able to dissolve only at least one intermediate in the reaction, in order to achieve a solution-solid reaction that is fairly efficient, reproducible, and therefore more scalable than a reaction between two different solids and a gas. A suitable solvent should be able to dissolve Pt(Hal)2(PF3) in situ from Pt(Hal)2 and PF3 under the reaction conditions. x The catalyst should be capable of dissolving at least one platinum-containing reaction intermediate such as (where Hal=F, Cl, Br or I; x=1, 2).

[0070] Platinum precursors may form soluble reaction intermediates in solvents under certain reaction conditions; in other cases, the addition of a solvent results in a lower yield of Pt(PF) compared to a solvent-free reaction (see Comparative Example 1(b)), where the yield of Pt(PF) is 60% in the solid-gas reaction and Example 7 (No. 9), and the yield of Pt(PF) is 26% in the reaction in hexadecane under the same pressure and temperature. The disclosed platinum precursors, Pt(Hal) (Hal = F, Cl, Br, or I), form soluble intermediates and are therefore suitable for the disclosed synthesis process.

[0071] Suitable solvents for use herein may be selected from ether, arene or alkane solvents. The preferred boiling point (BP) of the solvent may be above 150°C, preferably above 200°C. This is because the calculated boiling point of Pt(PF3)4 is "Vapor Pressure The temperature is approximately 77°C, calculated by the equation logP = 10.34-2610 / T (P is Torr, T is Kelvin) from "Measurements of Volatile Transition-Metal Complexes," R.D. Scanner, J.H. Satcher, Jr., Report (1989), UCRL-53937, which is necessary for efficient separation of the solvent and the product Pt(PF3)4. For example, hexadecane (BP: 285°C, melting point (MP): 18°C, and vapor pressure (VP): 0.07 Torr at 20°C), p-cymene (BP: 177°C, MP: -68°C) and VP: 1 Torr at 20° C.), dihexyl ether (BP: 223° C., MP: −43° C. and VP: 0.05 Torr at 20° C.), triethylene glycol dimethyl ether (BP: 216° C., MP: −45° C. and VP: 0.025 Torr at 20° C.), tetraethylene glycol dimethyl ether (BP: 275° C., MP: −30° C. and VP: 0.001 Torr at 20° C.) may be suitable for use as solvents in the disclosed Pt(Hal)2-M-PF3 synthesis system.

[0072] In one embodiment, the intermediate PtCl(PF) was isolated from the reaction of PtCl and PF in hexadecane and its identity was confirmed by analysis. PtCl(PF) was further reacted with copper and PF under the conditions disclosed in item 5 of Table 1 to produce Pt(PF).

[0073] PF3, PtCl2, PtCl2(PF3) x Anhydrous solvents must be used in the synthesis of Pt(PF3)4 because (x=1, 2) and Pt(PF3)4 react with moisture. The reaction with moisture results in by-products such as HCl, HF, and / or phosphorus oxofluorides and fluorophosphates that contaminate the product Pt(PF3)4. For example, if Pt(PF3)4 is placed in any glass container, HF can form SiF4. To prevent the formation of contaminants, commercially available solvents can be dried by contact with a desiccant.

[0074] FIG. 2a shows a flowchart of the disclosed Pt(Hal)-M-PF synthesis process for the synthesis of Pt(PF). The process begins with Pt(Hal) (Hal = F, Cl, Br, or I), and the metal powder (M) and PF. At reaction temperatures ranging from 20 to 180°C, Pt(Hal) (Hal = F, Cl, Br, or I) and the metal powder may not be soluble. For example, PtCl is not soluble at reaction temperatures ranging from 20 to 180°C. First, in step 202, a suspension of the starting materials, Pt(Hal) (Hal = F, Cl, Br, or I) and the metal powder is formed in an anhydrous solvent by dispersing Pt(Hal) (Hal = F, Cl, Br, or I) and the metal powder in the anhydrous solvent. An excess of PF3 gas is then introduced into the suspension of Pt(Hal)2 (Hal = F, Cl, Br or I) and metal powder, where preferably Hal = Cl, and then Pt(Hal)2 is PtCl2. Preferably, the metal powder is Cu powder.

[0075] Pt(Hal)2 (Hal = F, Cl, Br or I) is anhydrous and suspended in anhydrous solvents The solvent is dried with a desiccant to form an anhydrous solvent, which is used to mix with the starting materials, anhydrous Pt(Hal)2 and metal powder. The solvent or anhydrous solvent has the general formula (C n H 2n+1 )2O and H3C(O(CH2)2) n Oxyhydrocarbon solvents having the general formula (C n H 2n+1 ) x C6H 6-x (x≧1, n≧1), or an arene solvent having the general formula C n H 2n+2 The anhydrous solvent may be a hydrocarbon solvent such as an alkane solvent having n≧1. Suitable anhydrous solvents for use in the method of the present disclosure may be a dry alkane solvent selected from decane, di-, tri-, tetra-, penta-, and hexadecane, etc.; a dry arene solvent selected from xylene, mesitylene, cymene, pentylbenzene, diisopropylbenzene, diisobutylbenzene, etc.; a dry ether solvent selected from dibutyl ether, dihexyl ether, dioctyl ether, dimethyl ether of diethylene glycol, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, etc.; or an arene solvent selected from xylene, mesitylene, cymene, pentylbenzene, diisopropylbenzene, diisobutylbenzene, etc.; or a combination thereof. The ether solvent is preferably dibutyl ether, dihexyl ether, dioctyl ether, triethylene glycol dimethyl ether, or tetraethylene glycol dimethyl ether. The arene solvent is preferably xylene, mesitylene, cymene, pentylbenzene, diisopropylbenzene, or diisobutylbenzene. The alkane solvent is preferably di-, tri-, tetra-, penta-, and hexadecane, as well as the mixture of alkanes known as mineral oil. The anhydrous solvent used in the process of the present disclosure can be xylene or hexadecane.

[0076] In some embodiments, the solvent or anhydrous solvent can be xylene or hexadecane. The desiccant can be 3 Å or 4 Å molecular sieves. Pt(Hal)2 (Hal = F, Cl, Br, or I) in an anhydrous solvent, metal powder, and excess PF3 can form the soluble reaction intermediate Pt(Hal)2(PF3). x (x=1, 2; Hal=F, Cl, Br, or I) can be formed in step 204. As used herein, the solvent or anhydrous solvent is used to form the soluble reaction intermediate Pt(Hal)2(PF3). x (x=1, 2; Hal=F, Cl, Br, or I) must be soluble in PF3. Here, an excess of PF3 can be added to a suspension of Pt(Hal)2 (Hal=F, Cl, Br, or I) and metal powder. Thus, the soluble reaction intermediate Pt(Hal)2(PF3) x (x=1, 2; Hal=F, Cl, Br, or I) can be formed from Pt(Hal)2 (Hal=F, Cl, Br, or I) and excess PF3 at temperatures, for example, 80°C to 130°C, and low pressures, for example, 20 psig to 300 psig. The solvent is the intermediate Pt(Hal)2(PF3) x (x=1, 2; Hal=F, Cl, Br, or I) is selected to be able to dissolve Pt(Hal)2 (Hal=F, Cl, Br, or I), so that Pt(Hal)2 (Hal=F, Cl, Br, or I) reacts with excess PF3 to form the reaction intermediate Pt(Hal)2(PF3). x (x=1, 2; Hal=F, Cl, Br, or I) in an anhydrous solvent. In step 206, the reaction intermediate Pt(Hal)(PF) xA solution of (x=1, 2; Hal=F, Cl, Br, or I) can react with metal powder and PF gas (e.g., when Hal=Cl, the metal powder is Cu powder, and PtCl(PF) + 2Cu + 3PF = 2CuCl + Pt(PF)) to form Pt(PF). An excess of PF is used in this step. Then, in step 208, the produced Pt(PF) is separated and purified from unreacted starting materials, solvent, and reaction by-products, such as copper halides (e.g., CuCl, CuCl) and their complexes with PF. As shown in FIG. 1, the separation and purification step can be performed in a pre-evacuated trap and / or a metal trap to remove the remaining PF and solvent and reaction by-products. The remaining PF can be recycled for use as starting material. The metal trap can be made of metal, such as stainless steel, carbon steel, and stainless steel alloy 316. The purified product Pt(PF3)4 is then stored in a metal ampoule or vessel or container in step 210. The storage metal ampoule or vessel or container can be made of metal, such as stainless steel, carbon steel, and stainless steel alloy 316. Alternatively, the storage ampoule or vessel or The ampoule or container may be made of plastic. The inner surface of the ampoule or container may be passivated with PF3 or electropolished.

[0077] In the method of the present disclosure, PF3, PtCl2, PtCl2(PF3) xBecause (x=1, 2) and Pt(PF3)4 react with moisture, anhydrous solvents must be used for the synthesis of Pt(PF3)4. To prevent the formation of contaminants, commercially available solvents can be dried by contact with a desiccant selected from 3 Å or 4 Å molecular sieves or activated alumina. The solvent drying process can be achieved by contacting the solvent and desiccant, which can be achieved by a static process or a flow process. Prior to the drying step, the commercially available solvent may be degassed by passing an inert gas through it or by applying a vacuum-inert gas cycle, where the vacuum is in the range of 0.1 Torr to 100 Torr, preferably 0.5 to 10 Torr, and the inert gas is selected from N2, Ar, or He, which contain less than 1 ppm of oxygen and moisture. Alternatively, the commercially available solvent can be dried with a desiccant without degassing.

[0078] The disclosed synthesis method provides a practical and scalable synthesis of Pt(PF3)4 by adjusting and optimizing reaction conditions to favor the product Pt(PF3)4 in high yield and minimize the impact of side reactions. The disclosed synthesis method can be carried out in standard high-pressure reactors, such as Parr Instrument Company Reactor Series 4520, 4530, 4540, and 4540 (rated at 1900-5000 psig); pressure-rated glass reactors, such as Parr Instrument Company Series 5100 Glass Reactor (rated at 150 psig); or Büchiglas laboratory and test pressure reactors equipped with standard agitators and heaters.

[0079] In some embodiments, the disclosed synthetic methods for the synthesis, purification, and storage of Pt(PF3)4 can include the following steps: a) drying the solvent; b) dispersing a platinum compound having the general formula Pt(Hal)2 (Hal=Cl, Br, I), such as PtCl2, and a metal powder having a certain particle size, such as metallic copper powder, in a dry or anhydrous solvent in a flow reactor to form a mixture or suspension of Pt(Hal)2 (Hal=Cl, Br, I) and metallic copper powder; c) adding an excess amount of PF3 to the mixture or suspension; d) stirring the reaction mixture formed in step c) at the required temperature and required PF3 pressure (i.e., low PF3 pressure) that results in the following reaction and products: a. PtCl2(PF3) x Formation of (x=1, 2); b. PtCl2(PF3) x in a dry solvent; and c. PtCl2(PF3) x and the reaction of PF3 with metallic copper powder to form the product Pt(PF3)4; e) Purifying the product Pt(PF3)4 by distilling volatile species from the reaction mixture into a separate trap to achieve: i. Separation of unreacted starting materials, by-products, and solvents; and ii. Separation of the product Pt(PF3)4 from unreacted PF3. f) purifying the crude Pt(PF3)4 by distillation; g) recycling unreacted PF3 to step c); and h) Storing the purified product Pt(PF3)4 in a metal ampoule or container made of metal such as stainless steel, carbon steel, and stainless steel alloy 316, and the inner surface of the metal ampoule or container being passivated or electropolished with PF3.

[0080] Alternatively, the disclosed method for synthesizing Pt(PF) with platinum compound Pt(Hal) (wherein Hal = F, Cl, Br, or I) comprises the following steps: dispersing a platinum compound Pt(Hal)2 (wherein Hal = F, Cl, Br or I) in an anhydrous solvent to form a suspension of Pt(Hal)2; introducing an excess amount of PF3 into a suspension of Pt(Hal)2; The reaction of PF3 and Pt(Hal)2 produces the platinum compound Pt(Hal)2(PF3) x forming a solution of in an anhydrous solvent; Metal powder with a certain particle size and an additional excess amount of PF3 were mixed together to form Pt(Hal)2(PF3). x adding to the solution; and Pt(Hal)2(PF3) under reaction conditions x forming Pt(PF3)4 via reaction of PF3 and metal powder.

[0081] In this case, Pt(Hal)2(PF3) x is a reaction intermediate synthesized by suspending excess PF3 and Pt(Hal)2 in an anhydrous solvent. Again, the use of a solvent for the synthesis of Pt(PF3)4 is believed to be novel. To the best of our knowledge, no other method has been used to synthesize Pt(PF3)4 in a solvent to form the reaction intermediate Pt(Hal)2(PF3). x It has never been synthesized from any platinum compound containing Hal (Hal = F, Cl, Br or I; x = 1, 2).

[0082] Alternatively, the disclosed method for synthesizing Pt(PF) with platinum compound Pt(Hal) (wherein Hal = F, Cl, Br, or I) comprises the following steps: providing a metal powder having a uniform particle size; providing PF3 gas; At least one platinum-containing reaction intermediate Pt(Hal)2(PF3) formed from platinum precursors Pt(Hal)2 and PF3 under reaction conditions such as low pressures of 20 psig to 300 psig and temperatures ranging from 80°C to 130°C. x synthesizing Pt(PF) from metal powder, PF, and platinum compound Pt(Hal) (where Hal = F, Cl, Br, or I) in an anhydrous solvent capable of dissolving Pt(PF); and Purifying and storing Pt(PF3)4 in air- and moisture-free conditions in devices and ampoules made from metal or plastic.

[0083] Alternatively, the disclosed method for synthesizing Pt(PF) with platinum compound Pt(Hal) (wherein Hal = F, Cl, Br, or I) comprises the following steps: a) drying the solvent with a desiccant to form an anhydrous solvent; b) Adding a metal powder having a certain particle size, a platinum compound having the general formula Pt(Hal)2 (where Hal = F, Cl, Br, or I), and an excess amount of PF3 to an anhydrous solvent to obtain Pt(Hal)2(PF3). x where x=1, 2, and the anhydrous solvent is Pt(Hal)2(PF3) x The dissolvable step; c) Metal powders, PF3 and Pt(Hal)2(PF3) x in an anhydrous solvent to synthesize Pt(PF3)4; and d) Purifying the synthesized Pt(PF3)4 and storing the purified Pt(PF3)4 in devices and ampoules made from metal or plastic, such as stainless steel or plastic, under air- and moisture-free conditions.

[0084] Here, the plastic may be selected from polyethylene, polypropylene, styrene, Teflon, polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA).

[0085] As mentioned above, the reaction intermediate Pt(Hal)2(PF3) x (Hal = F, Cl, Br, or I; x = 1, 2) is soluble in hydrocarbon solvents and can be isolated and purified. The synthesis of Pt(PF3)4 is carried out by the platinum compound Pt(Hal)2(PF3) x (Hal = F, Cl, Br or I; x = 1, 2). Figure 2b shows the Pt(Hal)2(PF3) x3 is a flowchart of an exemplary process for synthesizing Pt(PF3)4 starting from (x=1, 2; Hal=F, Cl, Br, or I). As shown, in step 302, Pt(Hal)2(PF3) x (Hal = F, Cl, Br or I; x = 1, 2) solution is Pt(Hal)2(PF3) x (Hal = F, Cl, Br or I; x = 1, 2) in an anhydrous solvent. Preferably, Hal is Cl and Pt(Hal)2(PF3) x is PtCl2(PF) x Then, in step 304, a metal powder having a certain particle size is mixed with Pt(Hal)2(PF3) x (Hal = F, Cl, Br, or I; x = 1, 2) is introduced into the solution to form a suspension. Preferably, the metal powder is Cu powder with a certain particle size. Then, an excess amount of PF3 gas is introduced into the suspension in step 306. Then, Pt(Hal)2(PF3) xPt(PF) is formed in step 308 by reacting (x=1, 2; Hal=F, Cl, Br, or I) with metal powder and PF under low pressure. An excess of PF is used in this step. Then, in step 310, the resulting Pt(PF) is separated and purified from unreacted starting materials, solvent, and reaction by-products, such as copper halides (e.g., CuCl, CuCl) and their complexes with PF. As shown in FIG. 1, the separation and purification steps can be performed in a pre-evacuated trap and / or a metal trap to remove the remaining PF and solvent and reaction by-products. The remaining PF can be recycled for use as starting material. The metal trap can be made of metal, such as stainless steel, carbon steel, and stainless steel alloy 316. The purified product, Pt(PF), is then stored in a metal ampoule or vessel or container in step 312. The storage metal ampule or vessel or container may be made of metal, such as stainless steel, carbon steel, and stainless steel alloy 316. Alternatively, the storage ampule or vessel or container may be made of plastic. The interior surface of the ampule or vessel or container may be passivated with PF3 or electropolished.

[0086] Platinum compound Pt(Hal)2(PF3) x The disclosed method for synthesizing Pt(PF3)4 with Hal = F, Cl, Br, or I; x = 1, 2 comprises the following steps: Pt(Hal)2(PF3) x (Hal = F, Cl, Br or I; x = 1, 2) was dissolved in anhydrous solvent to prepare Pt(Hal)2(PF3). x forming a solution; Metal powder with a certain particle size and an excess amount of PF3 were mixed with Pt(Hal)2(PF3). x adding to the solution; and Pt(Hal)2(PF3) under reaction conditions of low pressure ranging from 20 psig to 300 psig and temperature ranging from 80°C to 130°C. x , forming Pt(PF3)4 by reaction of PF3 and metal powder.

[0087] Alternatively, the platinum compound Pt(Hal)2(PF3) x The disclosed method for synthesizing Pt(PF3)4 with Hal = F, Cl, Br, or I; x = 1, 2 comprises the following steps: a) drying the solvent with a desiccant to form an anhydrous solvent; b) Platinum compound Pt(Hal)2(PF3) x (wherein Hal = F, Cl, Br, or I; x = 1, 2), a metal powder having a certain particle size and an excess amount of PF3 are added to an anhydrous solvent to synthesize Pt(PF3)4, and the anhydrous solvent is Pt(Hal)2(PF3). x and c) Purifying the synthesized Pt(PF3)4 and storing the purified Pt(PF3)4 in an apparatus and ampoule made of metal, such as stainless steel, or plastic under air- and moisture-free conditions.

[0088] Here, plastics include polyethylene, polypropylene, styrene, Teflon, polytetrafluoroethylene (PTFE), and perfluoroalkoxyalkane (PFA). The metal may be selected from carbon steel, stainless steel, or stainless steel alloy 316. The metal powder may be Cu, Zn, or Al powder, etc.

[0089] The present disclosure also includes the purity of the product Pt(PF3)4 and a storage container for the product Pt(PF3)4. The product Pt(PF3)4 can be stored in a stainless steel and electropolished stainless steel container at room temperature without any change in purity. The disclosed method for synthesizing Pt(PF3)4 further includes the step of purifying the synthesized Pt(PF3)4: distilling the synthesized Pt(PF3)4 with a metal trap to remove the solvent and by-products, thereby forming by-product-free Pt(PF3)4; distilling the by-product-removed Pt(PF3)4 in a metal vessel to remove the solvent and residual PF3 to form purified Pt(PF3)4; and Optionally, recycling the remaining PF3 to synthesize Pt(PF3)4. Includes:

[0090] The disclosed method for synthesizing Pt(PF3)4 further comprises the step of storing the purified Pt(PF3)4: storing the purified Pt(PF3)4 in a metal (e.g., stainless steel) container or a metal (e.g., stainless steel) container with a passivated or electropolished interior surface at room temperature; Includes:

[0091] Here, the purity of purified Pt(PF3)4 stored in a metal container or a metal container with passivated or electropolished inner surface can remain constant. The containers are made of carbon steel, stainless steel, and stainless steel 316 alloy. The metal container can have an electropolished inner surface. Alternatively, Pt(PF3)4 can be stored in a plastic container. The plastic material can be polyethylene, polypropylene, styrene, Teflon, polytetrafluoroethylene (PTFE), or perfluoroalkoxyalkane (PFA).

[0092] The metal powder used in the method of the present disclosure is composed of a metal that has a lower electrode potential than platinum, does not interact with or form complexes with PF3 under the reaction conditions, and has an appropriate particle size range that allows it to maintain powder form during the reaction process.

[0093] Preferably, the metal powder is copper, zinc, aluminum powder, etc. Any metal and its halide that does not interact with or form a complex with PF3 under the reaction conditions and has an electrode potential lower than that of platinum (+1.2) can be used herein. For example, Cu (+0.34), Pb (-0.13), Sn (-0.14), Cd (-0.40), Zn (-0.76), and their halides do not interact with or form a complex with PF3 under the reaction conditions and can be used as the metal powder.

[0094] The following non-limiting examples are provided to further illustrate embodiments of the present invention, however, the examples are not intended to be all-inclusive and are not intended to limit the scope of the invention described herein. [Example]

[0095] Experimental method Reaction mixtures, starting materials, solvents, and products can be analyzed by any suitable means, such as gas chromatography, NMR, Raman, or FTIR spectroscopy, using portions or aliquots of the stream. All measurements were performed with samples in sealed containers, suitable test tubes, or ampoules, completely preventing contact with an oxygen- and moisture-containing atmosphere. High-purity liquid nitrogen, nitrogen gas, with O2 and water content below 0.1 ppm.

[0096] Reagents: Potassium hexachloroplatinate(IV) (KPtCl, Pt assay 40.1 ± 0.7%, CAS: 16921-30-5) was from Colonial Metals, Inc.; platinum(II) chloride (PtCl, Pt assay 73.3 ± 1.0%, CAS: 10025-65-7) was from Colonial Metals, Inc. Three copper powders were available: one from Strem Chemicals Inc. (99.999%) 100 mesh (100 mesh = 149 μm); another from Sigma-Aldrich (<425 μm, 99.5%); and another from Sigma-Aldrich (<45 μm, 99.99%). Phosphorus(III) fluoride (PF, CAS: 7783-55-3) was from Advance Research Chemicals, Inc. Molecular sieves, 3Å, beads, 4-8 mesh (Sigma-Aldrich) were regenerated in a dry nitrogen stream at temperatures between 300 and 350°C or under reduced pressure at temperatures between 300 and 350°C. After regeneration, the reaction was carried out under a nitrogen atmosphere with O2 and water contents below 0.5 ppm. The solvents, xylene and hexadecane, were from Sigma-Aldrich and were degassed and dried over 3Å molecular sieves. The reactor was filled with platinum compounds and copper powder under a nitrogen atmosphere with O2 and water contents below 0.5 ppm.

[0097] Example 1. Synthesis of Pt(PF3)4 with hexadecane solvent in a high-pressure reactor. Referring to Table 1 below, the amounts of PtCl2, Cu, and hexadecane used were loaded into a Parr Instrument Company reactor (Series 4540, 600 mL, 5000 psig rating) in a glove box. The reactor was removed, connected to a vacuum line, and depressurized to less than 0.3 Torr. The required amount of PF3 was introduced into the reactor at less than -79°C (Nos. 1-3) or at room temperature (No. 6). The reactor was then warmed to room temperature, stirring was initiated, and the temperature in the reactor was then increased to 105°C, and the reaction mixture was stirred under PF3 pressure. In Reaction No. 6, PF3 was added to the reactor in several portions during the reaction to maintain the pressure within the range of 100-200 psig. In all reactions, a pressure drop was observed at 105°C during the first 6 hours, followed by stabilization, indicating that the reaction may take approximately 6 hours. The pressure in the reactor was monitored for several more hours, then the reactor contents were cooled to 35-45°C, and a portion of the gas (approximately 25-35%) was sent to a pre-evacuated trap (0.44 L, stainless steel) cooled with a dry ice-isopropanol mixture. In Reaction 6, all pressure in the trap was released. The reactor was closed, and the trap was maintained for approximately 10 minutes. The non-condensable gas was then sent to a second trap (6 L, aluminum) cooled with liquid nitrogen. The transfer lines and valves were warmed by the passing gas if cooled below 0°C. After condensing the PF3 portion in the 6 L Al trap, a vacuum was applied to the 6 L Al trap to reduce the pressure in the trap to less than 1 Torr. This procedure was repeated until all PF3 and Pt(PF3)4 had been removed from the reactor and collected in two separate traps. The trap containing Pt(PF3)4 was then reconnected to another pre-evacuated vessel (0.4 L, electropolished stainless steel). The parent trap containing Pt(PF3)4 was warmed to room temperature while the receiving vessel was cooled with liquid nitrogen, and all the Pt(PF3)4 was distilled in the receiving vessel under static vacuum. After distillation, the receiving vessel was warmed to room temperature, and the remaining PF3 was released from the scrubber. The yields of Pt(PF3)4 are shown in Table 1 below.

[0098] [Table 1]

[0099] 1 H, 19 By F NMR, the purity of Pt(PF3)4 is >99% in all experiments. For example, in reaction 1, the purity of the neat product 19 F NMR (σCFCl3, ppm): -11.5 (m, J(PF) = 1302 Hz, 99.63%, Pt(PF3)4), -34.4 (d, J(PF) = 1402 Hz, 0.05%, PF3), -81.58 (0.19%, fluorophosphate, unassigned), -92.4 (d, J(PF) = 2035 Hz, 0.12%, POF3). 1 H NMR (σSiMe4, ppm): 0.90 and 1.32 (hexadecane), 13.1 (s, fluorophosphate). 1 H NMR analysis of hexadecane. 0.18 g of purified product was taken from reaction 1 and mixed with 0.77 g of C6D6 containing 0.03% (0.23 mg, 0.0026 mmol) of SiMe4. 1 H NMR (σSiMe4, ppm): 0.00 (s, 97.7 mol %, SiMe4), 1.32 (2.3 mol %, hexadecane), 7.16 (s, fluorophosphoric acid; relative intensities not measured for C6D6 because the water was not dried). Recalculating from mol% to wt%, taking into account that the solution contained 0.23 mg of TMS, the total amount of hexadecane in the Pt(PF3)4 sample was 0.014 mg, corresponding to 79 ppm in the Pt(PF3)4 from reaction 1.

[0100] Additional trap-to-trap distillation yields Pt(PF3)4 at 99.79% purity. 19 F NMR was measured in a glass ampoule (σCFCl3, ppm): -11.5 (m, J(PF) = 1302 Hz, 99.79%, Pt(PF3)4), -88.20 (d, J(PF) = 975 Hz, 0.19%, (HO)POF2), -92.4 (d, J(PF) = 2035 Hz, 0.01%, POF3) -166.1 (s, 0.02%, SiF4).1 H NMR (σSiMe4, ppm): 0.90 and 1.32 (hexadecane, relative intensity 28%), 12.94 (s, (HO)POF2, relative intensity 72%). The hexadecane resonances were below the detection limit for a solution of 0.07 g of sample in 0.78 g of C6D6 containing 0.03% SiMe4. The total amount of hexadecane is therefore less than 80 ppm. FTIR. [Liquid Pt(PF3)4 in Golden Gate™ probe, 4 cm resolution] -1 ]:882, 827, 496cm -1 .

[0101] Example 2. Synthesis of Pt(PF3)4 with isolation of PtCl2(PF3)2 and hexadecane solvent. a) PtCl2(PF3) in hexadecane x Composition of (x=1, 2). PtCl2 (1.9 g, 7.1 mmol) and hexadecane (15.8 g, 20.4 mL) were charged into a 150 mL pressure glass ampoule (Chemglass Life Sciences, part number CG-1880-31) equipped with a stir bar, thermocouple, and pressure gauge. The ampoule was connected to a vacuum line and a cylinder containing PF3. The ampoule containing the starting material was evacuated to approximately 0.2 Torr to remove nitrogen, and then 35 psig of PF3 was added, and the suspension was heated with stirring. The contents were stirred at temperatures ranging from 100 to 120 °C under 20 to 35 psig of PF3 for 4 hours, where PF3 was added in portions when the pressure approached 20 psig. During the reaction, PtCl2, which was initially insoluble in hexadecane, reacted completely with PF3, forming a compound soluble in hexadecane, some of which sublimed as colorless crystals in the cold section of the apparatus. After 4 hours, heating was stopped, the reaction mixture was cooled to room temperature, the PF3 was condensed back into the cylinder, and a portion of the crystals was separated from the solution and analyzed; a portion of the supernatant hexadecane solution was also 19 The crystals dissolved in pure anhydrous hexadecane were analyzed by F NMR. 19F NMR (σCFCl3, ppm): -36.4 (m, J(Pt-F) = 628 Hz, J(PF) = 1320 Hz, PtCl2(PF3)2). 19 F NMR(σCFCl3,ppm):-32.5(d,J(PF)=1405Hz,PF3),-36.4(m,J(Pt-F)=622Hz,J(PF)=1318Hz,PtCl2(PF3)2). Crystal FTIR (Golden Pure solids on a Gate™ probe, 4cm resolution -1 ):417(sh,w),447(sh,w),461(m),483(s),507(s),518(s),531(m),551(s),901(vs),907(sh),933(vs),961(s),969(w),974(m),985(w) DSC of crystals: 19.0℃ (phase transition), 72.5℃ (phase transition), 118.3℃ (melting point).

[0102] b) PtCl2(PF3) in hexadecane x Synthesis of Pt(PF3)4 from (x=1, 2). The colorless crystals from a) were placed in the supernatant hexane solution, copper (2.22 g, 34.9 mmol) was added, and an ampoule (150 mL HW pressure glass vessel) was connected to a vacuum line and a cylinder containing PF3. The ampoule containing the starting material was briefly evacuated to approximately 2 Torr to remove nitrogen, and then 40 psig of PF3 was added. The suspension was heated with stirring for 4 hours at temperatures ranging from 100 to 130 °C. The reaction was carried out under 20 to 40 psig of PF3, where PF3 was added in portions when the pressure approached 20 psig. After 4 hours, heating was stopped, the reaction mixture was cooled to 35 °C, and Pt(PF3)4, PF3, and some of the solvent were condensed in a liquid nitrogen-cooled stainless steel trap under static vacuum. Pt(PF3)4 was purified from PF3 and remaining hexadecane by trap-to-trap distillation. The yield of Pt(PF3)4 was 1.25 g (32%, low yield due to the use of PtCl2(PF3)2 and part of the supernatant solution in a) for analysis). 19F NMR (σCFCl3, ppm): -11.5 (m, J(PF) = 1301 Hz, Pt(PF3)4). 1 H NMR (σSiMe4, ppm): 0.23 (t, J=6.1Hz, 71.7mol.%, Me2SiF2), 0.90 and 1.32 (28.3mol.%, hexadecane).

[0103] Example 3. Synthesis of Pt(PF3)4 with hexadecane solvent in a glass ampoule. PtCl (8.75 g, 32.9 mmol), Cu (18.25 g, 287.2 mmol), and hexadecane (30.95 g, 40 mL) were charged into an ampoule (150 mL HW pressure glass vessel, part number CG-1880-31, from Chemglass Life Sciences) equipped with a stir bar, thermocouple, and pressure gauge. The ampoule was connected to a vacuum line and The ampoule containing the starting material was then evacuated to approximately 0.2 Torr to remove nitrogen, then 40 psig of PF3 was added, and the contents were heated with stirring. The contents were stirred at 20-50 psig of PF3 at a temperature ranging from 110 to 120 °C for 5.5 hours, with PF3 added in portions when the pressure approached 20 psig. During the reaction, crystals of PtCl2(PF3)2 formed and were then consumed; at the end of the reaction, the reaction mixture contained two immiscible liquids. After 5 hours and 30 minutes, heating was discontinued, the reaction mixture was cooled to 41 °C, and Pt(PF3)4, PF3, and some of the solvent were condensed in a liquid nitrogen-cooled stainless steel trap under static vacuum. Pt(PF3)4 was purified from PF3 and remaining hexadecane by trap-to-trap distillation. The yield of Pt(PF3)4 is 79% (14.2 g). 19 F NMR (σCFCl3, ppm): -11.5 (m, J(PF) = 1301 Hz, 99.40%, Pt(PF3)4), -34.4 (d, J(PF) = 1402 Hz, 0.36%, PF3), -92.4 (d, J(PF) = 2035 Hz, 0.23%, POF3), -166.0 (s, 0.007%, SiF4).1 H NMR(σSiMe4,ppm):0.23(t,J=6.1Hz,67.4mol.%,Me2SiF2),0.90 and 1.32(6.9mol.%,hexadecane),1.45(d,J=6.1Hz,25.8mol.%,P(O i Pr)3). 1 Determination of organic content by H NMR. The resonance intensities of organic compounds were below the detection limit for a solution of 0.09 g of Pt(PF3)4 sample dissolved in 0.76 g of C6D6 containing 0.03% (0.228 mg, 0.0026 mmol) of SiMe4. Therefore, the total amount of organic compounds is less than 80 ppm in Pt(PF3)4.

[0104] Example 4. Synthesis of Pt(PF3)4 in a glass ampoule applying xylene solvent. PtCl2 (2.19 g, 8.2 mmol), Cu (4.69 g, 73.8 mmol), and xylene (16.1 g) were charged into a 150 mL pressure glass ampoule (Chemglass Life Sciences, part number CG-1880-31) equipped with a stir bar, thermocouple, and pressure gauge. The ampoule was connected to a vacuum line and a cylinder containing PF3. The ampoule containing the starting materials was briefly evacuated to approximately 3 Torr to remove nitrogen, and then 40 psig of PF3 was added and the contents were heated with stirring. The contents were stirred at a temperature range of 100-120 °C under 20-40 psig of PF3 for 4.5 hours, where PF3 was added in portions when the pressure approached 20 psig. During the reaction, crystals of PtCl2(PF3)2 formed and then consumed; at the end of the reaction, the reaction mixture contained two immiscible liquids. After 4 hours and 30 minutes, heating was stopped, the reaction mixture was cooled to 38°C, and Pt(PF3)4, PF3, and some of the solvent were condensed in a liquid nitrogen-cooled trap (stainless steel) under static vacuum. Pt(PF3)4 was purified from PF3 and the remaining solvent xylene by trap-to-trap distillation. The yield of Pt(PF3)4 was 95% (4.3 g). 19F NMR (σCFCl3, ppm): -11.5 (m, J(PF) = 1301 Hz, 99.58%, Pt(PF3)4), -34.4 (d, J(PF) = 1402 Hz, 0.39%, PF3), -92.4 (d, J(PF) = 2035 Hz, 0.03%, POF3), -166.0 (s, 0.01%, SiF4). % is based on integration. 1 H NMR (σSiMe4, ppm): 0.12 (t, J = 6.1 Hz, 0.7 mol.%, Me2SiF2), 1.11 (t) and 2.56 (q) (18.8 mol.%, Et-C6H5), 2.05 (s) and 2.14 (s) (79.4 mol.%, xylene), 6.97 (m, aromatic protons), 12.46 (br, 1.0 mol.%, fluorophosphate). 1 Determination of residual solvent by H NMR. A 0.088 g sample of Pt(PF3)4 was taken and dissolved in 0.80 g of C6D6 containing 0.03% (0.24 mg, 0.0027 mmol) of SiMe4. 1 H NMR (σSiMe4, ppm): 0.00 (s, 6.28 mol.%, SiMe4), 1.07 (t) and 2.39 (q) (18.64 mol.%, Et-C6H5), 2.02 (s, 11.41 mol %, xylene), 2.14 (s, 63.67 mol %, xylene), 6.97 (m, aromatic protons). Recalculating from mol% to wt%, taking into account that the solution contained 0.24 mg of TMS, the total amount of organic compounds was 4.27 mg, which corresponds to 4.85 wt% in the 88 mg Pt(PF3)4 sample.

[0105] Example 5. Pt(PF3)4 Shelf Life Shelf life tests were carried out at room temperature for 12 weeks. Pt(PF3)4 was obtained by the synthesis described in Examples 3 and 4 and was dissolved in 50 cm 3 The samples were collected in a small sample cylinder of 316 alloy with a blind cap and one open end, and in a small canister made of electropolished stainless steel with a blind cap (V = 400 cm). 3 ) at room temperature. Before introducing Pt(PF3)4, both containers were vacuum baked at approximately 150 °C and 30–50 mTorr.19 F and 1 H NMR spectra were taken every two weeks on the undiluted Pt(PF3)4 to determine the Pt(PF3)4 assay and the relative amounts of impurities. 19 F and 1 The shelf life was monitored from H NMR spectra. The results of the shelf life tests are shown in Table 2.

[0106] [Table 2]

[0107] The Pt(PF3)4 assay and relative amounts of impurities are similar in all experiments over the 12-week period. The deviation is higher for the 316SS steel ampoules. These results demonstrate the stability of Pt(PF3)4 over time. Figure 4 is a graph of the Pt(PF3)4 assay and relative amounts of impurities over time at room temperature in a 400 mL electropolished stainless steel canister. The disclosed Pt(PF3)4 is intended for use as a precursor for Pt-containing films in the microelectronic device or catalytic industries.

[0108] Comparative Example 1. Synthesis of Pt(PF) starting from KPtCl using the recipe from Angew. Chem. Int. Ed. 1965, 4,521 and Russian Patent No. 2478576C2 The synthesis of Pt(PF3)4 according to the recipes from Angew. Chem. Int. Ed. 1965, 4,521 and Russian Patent No. 2478576C2 is shown in Table 3 below. The experiments were carried out in a commercially available high-pressure reactor (Series 4540, 600 mL, 5000 psig rating) manufactured by Parr Instrument Company, equipped with a standard impeller in experiments 10 and 12, and a U-shaped anchor stirrer designed for efficient mixing of the solids in experiment b). The process according to Russian Patent No. 2478576C2 utilizes pure hydrogen and a post-reduction drying step, which requires expensive, high-security equipment, and a long time, even if scale-up is possible to remove water from the system. As shown in Table 3, experiment 10 was carried out using 149 μm-sized copper powder, Cu (the copper powder was packaged in an argon atmosphere by the supplier and used as is). No. 11 and No. 12 are 425 μm size copper powder Cu (99.5%, Sig The synthesis of Pt(PF3)4 was carried out in a Sigma-Aldrich (product number 10-12). Starting from PtCl2 (product number 12, Table 3), the synthesis of Pt(PF3)4 was carried out according to [Angew. Chem. Int. Ed. 1965, 4, 521] with Cu (99.5%, Sigma-Aldrich) prepared from 425 μm copper powder. Pt(PF3)4 (product numbers 10-12) were formed in low to moderate yields.

[0109] Referring to Table 3, the comparative examples were performed using standard commercially available equipment. The starting materials, K2PtCl6, PtCl2, and Cu, were charged to a reactor in a glove box containing <0.5 ppm oxygen and moisture. The reactor was sealed, connected to a vacuum line, evacuated to less than 0.2 Torr, and cooled to less than -79°C. The required amount of PF3 was introduced into reactions 10-12 while stirring at low temperature. The reactor was then warmed to room temperature, then heated to 105-130°C, and the contents were stirred under PF3 pressure for 24 hours. The reactor contents were then cooled to 35-45°C, and a portion of the gas (approximately 25-35%) was sent to a pre-evacuated trap (0.44 L, stainless steel material) cooled with a dry ice-isopropanol mixture. The reactor was closed, the trap was maintained for approximately 10 minutes, and non-condensable gases were then sent to a second trap (6 L, aluminum material) cooled with liquid nitrogen. The transfer lines and valves were warmed by the passing gas if cooled below 0°C. After condensing the PF3 portion in the 6 L Al trap, a vacuum was applied to the 6 L Al trap until the pressure in the trap was less than 1 Torr. This procedure was repeated until all PF3 and Pt(PF3)4 had been removed from the reactor and collected in two separate traps. The trap containing Pt(PF3)4 was then reconnected to another pre-evacuated vessel (50 mL, stainless steel). The parent trap containing Pt(PF3)4 was warmed to room temperature, while the receiving vessel was cooled with liquid nitrogen. All Pt(PF3)4 was distilled into the receiving vessel under static vacuum. After distillation, the receiving vessel was warmed to room temperature, and the remaining PF3 was released from the scrubber. The yields of Pt(PF3)4 for each experiment were low to moderate, although Russian Patent No. 2478576C2 claimed yields of 60-95%. The low to moderate yield of Pt(PF3)4 obtained from the recipe of Russian Patent No. 2478576C2 may be due to the lack of solvent. The purity of Pt(PF3)4 is 1 H, 19 F NMR shows >97.9% in all experiments. For example, the yield of the neat product from experiment b) 19F NMR(σCFCl3,ppm): -11.5(m,J(PF)=1302Hz,97.9%,Pt(PF3)4), -34.4(d,J(PF)=1402Hz,0.2%,PF3), -92.4(d,J(PF)=2035Hz,2.0%,POF3).

[0110] [Table 3]

[0111] Example 6. Synthesis of Pt(PF3)4 starting from K2PtCl6 with hexadecane solvent in a high pressure reactor. K2PtCl6 (79.5 g, 0.16 mol), Cu (120.6 g, 1.9 mol), and hexadecane (100 g) were loaded into a reactor (Parr Instrument Company, Series 4540, 600 mL, 5000 psig rating) in a glove box. The reactor was removed, connected to a vacuum line, evacuated to 0.3 Torr, and cooled to below -79 °C. 387 g (4.4 mol) of PF3 was then introduced into the reactor. The reactor was then warmed to room temperature, the agitator was started, and the reactor was further heated to 120 °C. The contents were stirred under PF3 pressure for 22 h. The reactor contents were then cooled to 35-45 °C, and a portion of the gas (approximately 25-35%) was diverted to a pre-evacuated trap (0.44 L, stainless steel) cooled with a dry ice-isopropanol mixture. The reactor was closed, the trap was maintained for approximately 10 minutes, and then the noncondensable gases were sent to a second trap (6 L, aluminum material) cooled with liquid nitrogen. The transfer lines and valves were warmed by the passing gas if cooled below 0 °C. After condensing the PF3 portion in the 6 L Al trap, a vacuum was applied to the 6 L Al trap to reduce the pressure in the trap to less than 1 Torr. This procedure was repeated until all PF3 and Pt(PF3)4 had been removed from the reactor and collected in two separate traps. The trap containing Pt(PF3)4 was then reconnected to another pre-evacuated vessel (50 mL, stainless steel). The parent trap containing Pt(PF3)4 was warmed to room temperature, while the receiving vessel was cooled with liquid nitrogen, and all Pt(PF3)4 was distilled into the receiving vessel under static vacuum. After distillation, the receiving vessel was warmed to room temperature, and the remaining PF3 was released from the scrubber. The yield of Pt(PF3)4 was 23.2 g, 25.9% from K2PtCl6. See Table 4, which lists the yields of Pt(PF3)4 starting from K2PtCl6 in two reactions, this example and Comparative Example 1 above. Number 13 is from Comparative Example 1 above, while numbers 11 and 14 were the results for this example. Both reactions were at the same temperature and PF3 pressure. 19 Assay of Pt(PF3)4 by integration of the F NMR spectrum is 99.48%. 19F NMR(σCFCl3,ppm): -11.5(m,J(PF)=1302Hz,99.48%,Pt(PF3)4), -34.4(d,J(PF)=1402Hz,0.3%,PF3), -92.4(d,J(PF)=2035Hz,0.2%,POF3).

[0112] [Table 4]

[0113] The low yields associated with the use of PtCl2 in Table 3 may be due to inefficient mixing of the components, coating of the metal with metal chloride during the reaction, and other factors associated with reactions initiated from two different solids and gases. A solution may be to move from a solid-gas system to a solution-solid system to achieve better mixing of the components and more efficient interaction of the dissolved components in the liquid phase in which the metal powder is suspended. However, solution-solid systems have not been reported to date because it is expected that the solvent would undergo catalytic reactions with the Pt precursor or intermediate.

[0114] Although the subject matter described herein may be described in the context of example implementations for processing one or more computing application functions / operations for a computing application having a user-interactive component, the subject matter is not limited to these particular embodiments. Rather, the techniques described herein may be applied to any suitable type of user-interactive component execution management method, system, platform, and / or device.

[0115] It should be understood that many additional changes in the details, materials, steps and arrangements of parts described and illustrated herein to explain the nature of the invention may be made by those skilled in the art within the principles and scope of the invention as expressed in the appended claims. Therefore, the invention is not intended to be limited to the specific embodiments in the examples described above and / or in the accompanying drawings.

[0116] While embodiments of the present invention have been shown and described, modifications thereof can be made by those skilled in the art without departing from the spirit or teachings of the invention. The embodiments described herein are merely exemplary and not limiting. Many variations and modifications of compositions and methods are possible and within the scope of the present invention. Accordingly, the scope of protection is not limited to the embodiments described herein, but is limited only by the following claims, which scope is intended to include all equivalents of the subject matter of the claims. [Explanation of symbols]

[0117] 11 Cu powder 12 PtCl2 13 PF3 14 Solvents 15 containers 16 Reactor 17 Pre-depressurized trap 18 Pt(PF3)4 trap 19 Metal ampoules 20 PF3 Trap 101 Line 102 Dripping funnel 103 Addition Line 104 Drying Process 105 Line 106 Line 107 Line 108 Bypass 109 Packaging 110 Line

Claims

1. Pt(PF ３ ) ４ (CAS No. 19529-53-4), comprising the steps of: Platinum precursor Pt (Hal) ２ forming a suspension of Hal = F, Cl, Br or I and metal powder in a solvent; Excessive amount of PF ３ Pt(Hal) ２ and introducing said metal powder into said suspension; PF under reaction conditions ３ and Pt(Hal) ２ (wherein Hal = F, Cl, Br or I; x = 1, 2), to produce a soluble reaction intermediate Pt(Hal) ２ (PF ３ ) ｘ forming a Pt(Hal) in the solvent ２ (PF ３ ) ｘ , the metal powder and the excess amount of PF ３ Pt(PF ３ ) ４ Step of forming A method comprising:

2. The soluble reaction intermediate Pt(Hal) ２ (PF ３ ) ｘ (Hal=F, Cl, Br or I; x=1, 2), wherein the synthesizing step comprises: The platinum precursor Pt(Hal) ２ is dispersed in the solvent, and Pt(Hal) ２ forming a suspension of Hal; PF ３ Pt(Hal) ２ into said suspension; and The soluble reaction intermediate Pt(Hal) ２ (PF ３ ) ｘ (Hal = F, Cl, Br or I; x = 1, 2) in the above solvent, ３ and Pt(Hal) ２ 10. The method of claim 1, comprising forming via reaction:

3. The platinum precursor Pt(Hal) ２ The method of claim 1 , wherein is anhydrous.

4. The soluble reaction intermediate Pt(Hal) ２ (PF ３ ) ｘ 2. The method of claim 1, wherein (Hal = F, Cl, Br or I, x = 1, 2) is anhydrous.

5. The method of any one of claims 1 to 4, wherein the reaction conditions include a reaction temperature of less than about 200°C.

6. 5. The method of any one of claims 1 to 4, wherein the reaction conditions include a reaction pressure of less than approximately 300 psig.

7. The method according to any one of claims 1 to 4, wherein the metal powder is copper, zinc or aluminum powder.

8. The method of any one of claims 1 to 4, wherein the metal powder has a particle size in the range of 200 to 900 micrometers.

9. The method of any one of claims 1 to 4, wherein the solvent is an anhydrous solvent.

10. The method according to any one of claims 1 to 4, wherein the solvent has a boiling point above 150°C.

11. The solvent is a compound represented by the general formula (C ｎ H ２ｎ＋１ ) ２ O(n≧1) and H ３ C(O(CH ２ ) ２ ) ｎ OCH ３ (n≧1), an oxyhydrocarbon solvent having the general formula (C ｎ H ２ｎ＋１ ) ｘ C ６ H ６－ｘ (x≧1, n≧1) or an arene solvent having the general formula C ｎ H ２ｎ＋２ The method according to any one of claims 1 to 4, wherein the hydrocarbon solvent is selected from alkane solvents having n > 1.

12. Pt(PF ３ ) ４ The method according to any one of claims 1 to 4, wherein the yield of is in the range of approximately 70 to 99.9%.

13. Pt(PF ３ ) ４ The method according to any one of claims 1 to 4, wherein the purity of is approximately 90 to 99.9% by weight after purification.

14. Pt(PF ３ ) ４ (CAS No. 19529-53-4), comprising the steps of: a) the platinum precursor Pt(Cl) in a solvent selected from xylene or hexadecane ２ forming a suspension of b) Excessive amount of PF ３ Pt(Cl) ２ and introducing PF into the suspension. ３ and Pt(Cl) ２ By the reaction of Pt(Cl) ２ (PF ３ ) ｘ forming a solution of (x=1, 2) in said solvent; c) Copper powder was dissolved in Pt(Cl) ２ (PF ３ ) ｘ (x=1, 2) to said solution; and d) The copper powder, PF ３ and Pt(Cl) ２ (PF ３ ) ｘ from the reaction of less than about 300 psig of PF ３ Pt(PF) at pressure and reaction temperature below approximately 200°C. ３ ) ４ Step of forming A method comprising:

15. The method of claim 14, wherein the copper powder has a particle size in the range of 200 to 900 micrometers.

16. 15. The method of claim 14, wherein the solvent is an anhydrous solvent.

17. Pt(PF ３ ) ４ (CAS No. 19529-53-4), comprising the steps of: a) Platinum precursor Pt(Hal) ２ forming a suspension of Hal = F, Cl, Br or I and metal powder in a solvent; b) Excessive amount of PF ３ Pt(Hal) ２ and introducing the metal powder into the suspension; and c) Pt(Hal) in said solvent under reaction conditions ２ , the metal powder and the excess amount of PF ３ Pt(PF ３ ) ４ Step of forming A method comprising:

18. PF ３ and Pt(Hal) ２ (wherein Hal = F, Cl, Br or I; x = 1, 2), to produce a soluble reaction intermediate Pt(Hal) ２ (PF ３ ) ｘ The method of claim 17 further comprising forming:

19. The soluble reaction intermediate Pt(Hal) ２ (PF ３ ) ｘ and the Pt(Hal) ２ 19. The method of claim 18, wherein is anhydrous.

20. The soluble reaction intermediate Pt(Hal) ２ (PF ３ ) ｘ (Hal=F, Cl, Br or I; x=1, 2), wherein the synthesizing step comprises: The platinum precursor Pt(Hal) ２ is dispersed in the solvent, and Pt(Hal) ２ forming a suspension of PF ３ Pt(Hal) ２ into said suspension; and The soluble reaction intermediate Pt(Hal) ２ (PF ３ ) ｘ (Hal = F, Cl, Br or I; x = 1, 2) in the above solvent, ３ and Pt(Hal) ２ 20. The method of claim 17, comprising forming via reaction:

21. The soluble reaction intermediate Pt(Hal) ２ (PF ３ ) ｘ and the platinum precursor Pt(Hal) ２ 21. The method of claim 20, wherein is anhydrous.

22. 22. The method of any one of claims 17 to 21, wherein the reaction conditions include a reaction temperature of less than about 200°C.

23. 22. The method of any one of claims 17 to 21, wherein the reaction conditions include a reaction pressure of less than about 300 psig.

24. The method according to any one of claims 17 to 21, wherein the metal powder is copper, zinc or aluminium powder.

25. 22. The method of any one of claims 17 to 21, wherein the metal powder has a particle size in the range of 200 to 900 micrometers.

26. The method of any one of claims 17 to 21, wherein the solvent is an anhydrous solvent.

27. The method of any one of claims 17 to 21, wherein the solvent has a boiling point above 150°C.

28. The solvent is a compound represented by the general formula (C ｎ H ２ｎ＋１ ) ２ O(n≧1) and H ３ C(O(CH ２ ) ２ ) ｎ OCH ３ (n≧1), an oxyhydrocarbon solvent having the general formula (C ｎ H ２ｎ＋１ ) ｘ C ６ H ６－ｘ (x≧1, n≧1) or an arene solvent having the general formula C ｎ H ２ｎ＋２ The method according to any one of claims 17 to 21, wherein the hydrocarbon solvent is selected from alkane solvents having n > 1.

29. Pt(PF ３ ) ４ The method of any one of claims 17 to 21, wherein the yield of is in the range of approximately 70 to 99.9%.

30. Pt(PF ３ ) ４ The method according to any one of claims 17 to 21, wherein the purity of is approximately 90 to 99.9% by weight after purification.

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