CN109206459B - Preparation method of tetraammineplatinum acetate (II) - Google Patents
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- CN109206459B CN109206459B CN201811094140.4A CN201811094140A CN109206459B CN 109206459 B CN109206459 B CN 109206459B CN 201811094140 A CN201811094140 A CN 201811094140A CN 109206459 B CN109206459 B CN 109206459B
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- acetate
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- oxalate
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 49
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 37
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000001639 calcium acetate Substances 0.000 claims abstract description 18
- 235000011092 calcium acetate Nutrition 0.000 claims abstract description 18
- 229960005147 calcium acetate Drugs 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 13
- QCSGLAMXZCLSJW-UHFFFAOYSA-L platinum(2+);diacetate Chemical compound [Pt+2].CC([O-])=O.CC([O-])=O QCSGLAMXZCLSJW-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- HNKLPNDFOVJIFG-UHFFFAOYSA-N oxalic acid;platinum Chemical compound [Pt].OC(=O)C(O)=O HNKLPNDFOVJIFG-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910014813 CaC2 Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- MUTQTHUBSRXFQO-UHFFFAOYSA-L oxalate;platinum(2+) Chemical compound [Pt+2].[O-]C(=O)C([O-])=O MUTQTHUBSRXFQO-UHFFFAOYSA-L 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 11
- -1 nitrate ions Chemical class 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 5
- 229910002651 NO3 Inorganic materials 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- 239000004332 silver Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000001514 detection method Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical class C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical class [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 2
- 229940071536 silver acetate Drugs 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
- C07F15/0093—Platinum compounds without a metal-carbon linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of tetraammineplatinum acetate (II). The preparation method comprises the following steps: ammonium chloroplatinate (IV) reacts with oxalic acid, ammonia water and calcium acetate in sequence in three steps to generate a tetrammine platinum (II) acetate solution, the tetrammine platinum (II) acetate solution is concentrated and then crystallized by a solvent to obtain tetrammine platinum (II) acetate crystals, and the tetrammine platinum (II) acetate crystals with the purity of more than or equal to 99.95 percent are obtained by vacuum drying. The initial raw material ammonium chloroplatinate (IV) is a conventional compound of platinum, the raw material is easy to obtain and has high yield, and other auxiliary materials, namely oxalic acid, strong ammonia water and calcium acetate, are cheap, so that the production cost is greatly reduced; in addition, the method not only avoids the residue of chloride ions and nitrate ions, but also reduces the residue of silver ions in the product. The method is carried out at normal temperature and normal pressure, is simple to operate, easy to control, high in reaction yield (more than 92%), high in product purity (more than or equal to 99.95%), and suitable for batch and industrial production of tetraammineplatinum (II) acetate.
Description
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to a preparation method of tetraammineplatinum acetate (II).
Background
The platinum catalyst is widely applied to various fields of petrochemical industry, pharmaceutical industry, automobile exhaust, environmental management and the like, and the high temperature resistance, the activity and the service life of equipment of the platinum catalyst are influenced due to the residues of chloride ions and nitrate ions in a precursor compound for preparing the platinum catalyst, along with the increasing use amount of the platinum catalyst, the requirement of people on the platinum catalyst is higher and higher, and the requirement on the residues of the chloride ions and the nitrate ions is lower and better.
The tetrammine platinum (II) compounds are important platinum (II) compounds and are widely applied to chemical catalysis and electroplating industries. Wherein the tetraammineplatinum (II) acetate (Pt (NH)3)4(CH3COO)2) The catalyst is very soluble in water and insoluble in organic solvents such as alcohols, ketones and the like, is the highest in solubility in the mainstream tetramine compounds at present, is very suitable for preparing the platinum catalyst by an immersion method, and the aqueous solution of the catalyst contains acetate which can play a buffering role at the same time and is also researched to be used as electroplating main salt, so that the vinegar is used as electroplating main saltTetraamineplatinum (II) acid is becoming an important class of platinum precursor compounds. The patent with publication number CN103113412A discloses a water-soluble Pt (II) catalytic precursor without chlorine and silver nitrate and a synthesis method thereof, wherein tetraammineplatinum chloride is used as a starting material and reacts with silver acetate to obtain a target compound tetraammineplatinum acetate. In the method, the tetrammine platinum dichloride is not easy to obtain, so the cost is higher and the yield is not high; in addition, the preparation method is limited because the price of silver acetate is expensive, the dosage is large, and silver ions are easy to remain in the product.
Disclosure of Invention
The invention aims to provide a preparation method of tetraammineplatinum acetate (II), wherein the starting material ammonium chloroplatinate (IV) is a conventional compound of platinum, the raw material is easy to obtain and has high yield, and other auxiliary materials of oxalic acid, strong ammonia water and calcium acetate are cheap, so that the production cost can be reduced; in addition, the method can not only avoid the residue of chloride ions and nitrate ions, but also reduce the residue of silver ions in the product.
In order to realize the purpose, the preparation method of the tetraammineplatinum acetate (II) comprises the following steps of sequentially reacting ammonium chloroplatinate (IV) with oxalic acid, ammonia water and calcium acetate in three steps, crystallizing by using a solvent, and drying to generate the tetraammineplatinum acetate (II), wherein the specific reaction steps are as follows:
(1) reducing ammonium chloroplatinate (IV) with oxalic acid to obtain diammineplatinum oxalate (II) solution, wherein the reaction formula is as follows:
(NH4)2PtCl6+2H2C2O4＝Pt(NH3)2(C2O4)+6HCl+2CO2
(2) ammoniation of diammine platinum oxalate (II) by strong ammonia water to obtain tetrammine platinum oxalate (II) solution, wherein the reaction formula is as follows:
Pt(NH3)2(C2O4)+2NH3·H2O＝Pt(NH3)4(C2O4)+2H2O
(3) adding calcium acetate into tetrammine platinum (II) oxalate to obtain tetrammine platinum (II) acetate solution and calcium oxalate, wherein the reaction formula is as follows:
Pt(NH3)4(C2O4)+Ca(CH3COO)2＝Pt(NH3)4(CH3COO)2+CaC2O4
(4) filtering the tetrammine platinum (II) acetate solution, carrying out rotary evaporation and concentration, crystallizing and separating out a solvent to obtain tetrammine platinum (II) acetate crystals, and carrying out vacuum drying to obtain the tetrammine platinum (II) acetate with the purity of more than or equal to 99.95%.
Preferably, the mass ratio of ammonium chloroplatinate (IV) to oxalic acid in the step (1) is 1: (0.4-0.7) and the reaction temperature is 30-50 ℃.
Preferably, the mass ratio of diammine platinum oxalate (II) to concentrated ammonia water in the step (2) is 1: (3-5), and controlling the reaction temperature to be 50-60 ℃ under stirring.
Preferably, the weight ratio of the tetraammineplatinum oxalate (II) to the calcium acetate in the step (3) is 1: (1-1.2).
Preferably, the tetraammineplatinum (II) acetate solution obtained in the step (4) is filtered to remove insoluble substances, the filtrate is directly concentrated under reduced pressure to obtain a concentrated solution, the concentrated solution is added into an alcohol or ketone organic solvent under stirring to obtain white crystals, and the volume ratio of the alcohol or ketone organic solvent to the tetraammineplatinum (II) acetate solution is (15-20): and 1, filtering and washing the white crystals, and drying the white crystals in vacuum at 50-80 ℃ to obtain tetraammineplatinum acetate (II).
Compared with the prior art, the initial raw material ammonium chloroplatinate (IV) is a conventional compound of platinum, the raw material is easy to obtain and has high yield, and other auxiliary materials, namely oxalic acid, strong ammonia water and calcium acetate, have low prices, so that the production cost is greatly reduced; in addition, the method not only avoids the residue of chloride ions and nitrate ions, but also reduces the residue of silver ions in the product. The tetraammineplatinum acetate (II) prepared by the method has high water solubility, and the compound undergoes dissociation reaction in aqueous solution to release stable complex cation Pt (NH)3)4 2+The carrier is favorable for adsorbing precursor compounds during impregnation, in addition, the aqueous solution of the carrier also contains acetate, and the carrier can play a buffering role at the same time, and the carrier is also used as electroplating main salt for research. The method of the invention is carried out in the usual wayThe reaction is carried out at normal temperature and pressure, the operation is simple, the control is easy, and the reaction yield is high>92 percent) and high product purity (more than or equal to 99.95 percent), and is suitable for batch and industrial production of the tetramine platinum (II) acetate.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example one
A preparation method of tetraammineplatinum acetate (II) comprises the following steps:
weighing 4.0g (0.044mol) of oxalic acid into a 300mL beaker, adding 50mL of deionized water, stirring to dissolve, slowly adding 10.0g (0.023mol) of ammonium chloroplatinate solid in portions, stirring at 30 ℃ to react for 2h, stopping stirring, standing for 10min, and filtering to obtain diammineplatinum (II) oxalate solution (7.3 g). Slowly adding 25mL (22.7g) of ammonia water into the diammine platinum oxalate (II) solution, controlling the temperature at 50-60 ℃, reacting for 2h, stopping heating, cooling to room temperature, dissolving 8g of calcium acetate in 25mL of deionized water to dissolve the calcium acetate, then slowly adding calcium acetate solution into tetraammineplatinum oxalate (8.0g) solution until no precipitate is generated, adding 5mL acetic acid, stirring for 0.5h, standing for 30min to obtain tetraammineplatinum acetate solution and white precipitate calcium oxalate, filtering, washing with deionized water for 2 times, mixing the filtrate with washing water, concentrating at 80 deg.C under reduced pressure to obtain 15mL concentrated solution, adding 3mL acetic acid, and then adding the concentrated solution added with acetic acid into 300mL of methanol solution to separate out white crystals, filtering, washing with methanol, and drying at 50-80 ℃ for 2h to obtain 7.95g of tetraammineplatinum acetate with the yield of 92.2%. Product detection: the chlorine content was 7.6 ppm.
The prepared sample is respectively subjected to element analysis, infrared spectrum detection, hydrogen spectrum detection and carbon spectrum detection, and the structural characteristic parameters are as follows: (1) elemental analysis: the measured values C12.52%, H4.65%, N14.6%, Pt 50.98% agree with the theoretical values C12.59%, H4.76%, N14.69%, Pt 51.17%. (2) IR (cm)-1，KBr) 3259，3220(s，v(NH3))；1695，1653(s，vas(C＝O))。1406(s，vs(C＝O))。 (3)1HNMR(D2O，ppm)1.75(s，3H，CH3)。(4)13C NMR(D2O，ppm) 23.7(CH3) 181.9 (COO). These parameters correspond to the chemical structure of the inventive compounds.
Example two
A preparation method of tetraammineplatinum acetate (II) comprises the following steps:
50.0g (0.555mol) of oxalic acid is weighed into a 2000mL beaker, 600mL of deionized water is added and stirred to dissolve, then 100.0g (0.225mol) of ammonium chloroplatinate solid is slowly added in portions, stirred and reacted for 1.5h at the temperature of 40 ℃, the stirring is stopped, and the solution (71.3g) of diammineplatinum oxalate (II) is obtained after standing for 10min and filtering. Slowly adding 320mL (291g) of ammonia water into the diammineplatinum oxalate (II) solution, controlling the temperature at 50-60 ℃, reacting for 2h, stopping heating, cooling to room temperature, dissolving 86.9g of calcium acetate in 300mL of deionized water to dissolve the calcium acetate, then slowly adding calcium acetate solution into tetrammine platinum oxalate (79.0g) solution until no precipitate is generated, adding 30mL acetic acid, stirring for 0.5h, standing for 30min to obtain tetrammine platinum acetate solution and white precipitate calcium oxalate, filtering, washing with deionized water for 2 times, mixing the filtrate with washing water, concentrating at 80 deg.C under reduced pressure to obtain 100mL concentrated solution, adding 5mL acetic acid, then adding the concentrated solution added with acetic acid into 2000mL of methanol solution, separating out white crystals, filtering, washing with methanol, and drying at 50-80 ℃ for 2h to obtain 80.06g of tetramine platinum acetate with the yield of 92.8%. Product detection: the chlorine content was 7.2 ppm.
The prepared sample is respectively subjected to element analysis, infrared spectrum detection, hydrogen spectrum detection and carbon spectrum detection, and the structural characteristic parameters are as follows: (1) elemental analysis: the measured values C12.54%, H4.63%, N14.62%, Pt 50.96% are in agreement with the theoretical values C12.59%, H4.76%, N14.69%, Pt 51.17%. (2) IR (cm)-1，KBr) 3259，3220(s，v(NH3))；1695，1653(s，vas(C＝O))。1406(s，vs(C＝O))。 (3)1HNMR(D2O，ppm)1.75(s，3H，CH3)。(4)13C NMR(D2O，ppm) 23.7(CH3) 181.9 (COO). These parameters correspond to the chemical structure of the inventive compounds.
EXAMPLE III
A preparation method of tetraammineplatinum acetate (II) comprises the following steps:
140g (1.555mol) of oxalic acid is weighed into a 5000mL beaker, 1000mL of deionized water is added, stirring is carried out for dissolution, then 200g (0.451mol) of ammonium chloroplatinate solid is slowly added in portions, stirring is carried out for reaction for 1h at the temperature of 50 ℃, stirring is stopped, standing is carried out for 10min, and filtration is carried out, thus obtaining diammineplatinum (II) oxalate solution (143.0 g). Slowly adding 785mL (715g) of ammonia water into the diammine platinum oxalate (II) solution, controlling the temperature at 50-60 ℃, reacting for 3h, stopping heating, cooling to room temperature, dissolving 190g of calcium acetate in 600mL of deionized water to dissolve, then slowly adding calcium acetate solution into tetrammine platinum oxalate (158.3g) solution until no precipitate is generated, adding 50mL acetic acid, stirring for 0.5h, standing for 30min to obtain tetrammine platinum acetate solution and white precipitate calcium oxalate, filtering, washing with deionized water for 2 times, mixing the filtrate with washing water, concentrating at 80 deg.C under reduced pressure to obtain 180mL concentrated solution, adding 10mL acetic acid, then adding the concentrated solution added with acetic acid into 3000mL of acetone solution, separating out white crystals, filtering, washing with methanol, and drying at 50-80 ℃ for 2h to obtain 159.6g of tetraammineplatinum acetate with the yield of 92.84%. Product detection: the chlorine content was 7.4 ppm.
The prepared sample is respectively subjected to element analysis, infrared spectrum detection, hydrogen spectrum detection and carbon spectrum detection, and the structural characteristic parameters are as follows: (1) elemental analysis: the measured values C12.56%, H4.62%, N14.60%, Pt 51.06% are in agreement with the theoretical values C12.59%, H4.76%, N14.69%, Pt 51.17%. (2) IR (cm)-1，KBr) 3259，3220(s，v(NH3))；1695，1653(s，vas(C＝O))。1406(s，vs(C＝O))。 (3)1HNMR(D2O，ppm)1.75(s，3H，CH3)。(4)13C NMR(D2O，ppm) 23.7(CH3) 181.9 (COO). These parameters correspond to the chemical structure of the inventive compounds.
Claims (5)
1. A preparation method of tetraammineplatinum acetate (II) is characterized in that ammonium chloroplatinate (IV) is sequentially reacted with oxalic acid, strong ammonia water and calcium acetate in three steps, and then is crystallized by a solvent and dried to generate tetraammineplatinum acetate (II), and the specific reaction steps are as follows:
(1) reducing ammonium chloroplatinate (IV) with oxalic acid to obtain diammineplatinum oxalate (II) solution, wherein the reaction formula is as follows:
(NH4)2PtCl6 + 2H2C2O4 = Pt(NH3)2(C2O4) + 6HCl + 2CO2
(2) ammoniation of diammine platinum oxalate (II) by strong ammonia water to obtain tetrammine platinum oxalate (II) solution, wherein the reaction formula is as follows:
Pt(NH3)2(C2O4) + 2NH3·H2O = Pt(NH3)4(C2O4) + 2H2O
(3) adding calcium acetate into tetrammine platinum (II) oxalate to obtain tetrammine platinum (II) acetate solution and calcium oxalate, wherein the reaction formula is as follows:
Pt(NH3)4C2O4 + Ca(CH3COO)2 = Pt(NH3)4(CH3COO)2 + CaC2O4
(4) filtering the tetrammine platinum (II) acetate solution, carrying out rotary evaporation and concentration, crystallizing and separating out a solvent to obtain tetrammine platinum (II) acetate crystals, and carrying out vacuum drying to obtain the tetrammine platinum (II) acetate with the purity of more than or equal to 99.95%.
2. The method for preparing tetraammineplatinum acetate (II) according to claim 1, wherein the mass ratio of ammonium chloroplatinate (IV) to oxalic acid in step (1) is 1: (0.4-0.7) and the reaction temperature is 30-50 ℃.
3. The method for preparing tetraammineplatinum acetate (II) according to claim 1 or 2, wherein the mass ratio of diammineplatinum oxalate (II) to concentrated ammonia water in step (2) is 1: (3-5), and controlling the reaction temperature to be 50-60 ℃ under stirring.
4. The method for preparing tetraammineplatinum acetate (II) according to claim 1 or 2, wherein the weight ratio of tetraammineplatinum oxalate (II) to calcium acetate in step (3) is 1: (1-1.2).
5. The preparation method of tetraammineplatinum acetate (II) according to claim 1 or 2, characterized in that the tetraammineplatinum acetate (II) solution obtained in step (4) is filtered to remove insoluble substances, the filtrate is directly concentrated under reduced pressure to obtain a concentrated solution, the concentrated solution is added into an alcohol or ketone organic solvent under stirring to obtain white crystals, and the volume ratio of the alcohol or ketone organic solvent to the tetraammineplatinum acetate (II) solution is (15-20): and 1, filtering and washing the white crystals, and drying the white crystals in vacuum at 50-80 ℃ to obtain tetraammineplatinum acetate (II).
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| CN201811094140.4A CN109206459B (en) | 2018-09-19 | 2018-09-19 | Preparation method of tetraammineplatinum acetate (II) |
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| CN201811094140.4A CN109206459B (en) | 2018-09-19 | 2018-09-19 | Preparation method of tetraammineplatinum acetate (II) |
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| CN109206459A CN109206459A (en) | 2019-01-15 |
| CN109206459B true CN109206459B (en) | 2021-03-02 |
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| CN112939100B (en) * | 2021-03-15 | 2021-11-09 | 徐州浩通新材料科技股份有限公司 | Preparation method of tetraammine palladium (II) bicarbonate |
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| SU1631980A1 (en) * | 1988-10-21 | 1996-09-27 | МГУ им. М.В.Ломоносова | Process for preparing oxalatodiaminoplatinum (ii) |
| CN101255176A (en) * | 2008-04-03 | 2008-09-03 | 昆明贵金属研究所 | Novel precursor compound for preparing platinum-carrying catalyst and synthetic method thereof |
| CN101389637A (en) * | 2006-01-30 | 2009-03-18 | 普拉托技术（私有）公司 | Preparation of platinum (ll) complexes |
| CN103113412A (en) * | 2013-01-31 | 2013-05-22 | 昆明贵金属研究所 | Water soluble Pt(II) catalyst precursor free from chlorine and nitrate and synthetic method thereof |
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| SU1631980A1 (en) * | 1988-10-21 | 1996-09-27 | МГУ им. М.В.Ломоносова | Process for preparing oxalatodiaminoplatinum (ii) |
| CN101389637A (en) * | 2006-01-30 | 2009-03-18 | 普拉托技术（私有）公司 | Preparation of platinum (ll) complexes |
| CN101255176A (en) * | 2008-04-03 | 2008-09-03 | 昆明贵金属研究所 | Novel precursor compound for preparing platinum-carrying catalyst and synthetic method thereof |
| CN103113412A (en) * | 2013-01-31 | 2013-05-22 | 昆明贵金属研究所 | Water soluble Pt(II) catalyst precursor free from chlorine and nitrate and synthetic method thereof |
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