CN105585596A - Preparation method of rhodium compounds - Google Patents
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- CN105585596A CN105585596A CN201510895747.2A CN201510895747A CN105585596A CN 105585596 A CN105585596 A CN 105585596A CN 201510895747 A CN201510895747 A CN 201510895747A CN 105585596 A CN105585596 A CN 105585596A
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- octadiene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000003284 rhodium compounds Chemical class 0.000 title claims abstract description 17
- -1 bis(1.5-cyclooctadiene) rhodium(I) tetrafluoroborate compounds Chemical class 0.000 claims abstract description 28
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 9
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical class O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 claims description 5
- 229910001630 radium chloride Inorganic materials 0.000 claims description 5
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 4
- UQYHZAKLQZQSGP-UHFFFAOYSA-N boric acid silver Chemical compound [Ag].B(O)(O)O UQYHZAKLQZQSGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims 2
- 229910052705 radium Inorganic materials 0.000 claims 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- TYLYVJBCMQFRCB-UHFFFAOYSA-K trichlororhodium;trihydrate Chemical compound O.O.O.[Cl-].[Cl-].[Cl-].[Rh+3] TYLYVJBCMQFRCB-UHFFFAOYSA-K 0.000 abstract 1
- 239000010948 rhodium Substances 0.000 description 10
- 238000002390 rotary evaporation Methods 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000007037 hydroformylation reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- GJMJIOGYTAVWAV-UHFFFAOYSA-N [Rh].B(O)(O)O Chemical compound [Rh].B(O)(O)O GJMJIOGYTAVWAV-UHFFFAOYSA-N 0.000 description 2
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001228 spectrum 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
- C07F15/0073—Rhodium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of rhodium compounds. According to the method, bis(1.5-cyclooctadiene) rhodium(I) tetrafluoroborate compounds are synthesized in two steps, firstly, 1.5-cyclooctadiene rhodium chloride dimmers are synthesized with rhodium chloride trihydrate as raw materials; secondly, the bis(1.5-cyclooctadiene) rhodium(I) tetrafluoroborate compounds are synthesized with the 1.5-cyclooctadiene rhodium chloride dimmers as raw materials. The one-way total yield is 93% or above, operation is easy, industrial production can be achieved, and certain economic benefits are achieved.
Description
Technical field
The invention belongs to organic catalysis noble metal catalyst preparing technical field, be specifically related to a kind of preparation method of rhodium compound.
Technical background
Rhodium compound is as noble metal homogeneous catalysis agent, to be widely used in hydroformylation, hydrogenation, the carbonyl important chemical process such as synthetic. For example: three (triphenylphosphine) radium chloride is as efficient olefin hydrogenation catalyst at industrial application, and rhodium dicarbonyl acetylacetonate, triphenylphosphine acetylacetone,2,4-pentanedione rhodium carbonyl, three (triphenylphosphine) carbonyl hydrogen rhodium etc. use in olefin hydroformylation commercial plant as efficient olefin hydroformylation catalyst.
At present about two (1,5-cyclo-octadiene) preparation method of tetrafluoro boric acid rhodium compound, be all that documents few in number are reported the preparation in its laboratory, and yield is on the low side, the rhodium metal more expensive for price and resource is few, is unfavorable for producing.
Summary of the invention
The object of this invention is to provide two 1,5-cyclo-octadiene tetrafluoro boric acid rhodium compounds and preparation method. Technical problem to be solved by this invention is, for above-mentioned the deficiencies in the prior art, to provide a kind of preparation method of rhodium compound. The method is simple to operate, and purity is high, and productive rate is high. Rhodium compound prepared by the method is widely used as catalyst in symmetrical and asymmetric hydrogenation reaction, hydroformylation, hydrosilylation and coupling reaction, and presents good catalytic action.
The object of the invention is to be achieved through the following technical solutions
A kind of preparation method of rhodium compound, the method is divided into two steps and synthesizes two (1,5-cyclo-octadiene) tetrafluoro boric acid rhodium compound, the first step, taking three rhodium trichloride hydrates as raw material, is synthesized 1,5-cyclo-octadiene radium chloride dimer, second step is with 1,5 cyclo-octadiene radium chloride dimers are raw material, synthetic two (1,5-cyclo-octadiene) tetrafluoro boric acid rhodium compounds.
First step reaction generates 1,5-cyclo-octadiene radium chloride dimer, and described method is divided into following step:
Step a: three rhodium trichloride hydrates are dissolved in organic solvent and water, obtain the A solution of rhodium chloride.
Step b: under nitrogen protection, 1,5-cyclo-octadiene is added drop-wise in A solution, is warming up to backflow, then at insulated and stirred reaction 12-36 hour.
Step c: cold filtration, filtrate is concentrated into certain volume and separates out solid and refilter, and combining solid vacuum drying obtains 1,5-cyclo-octadiene radium chloride dimer.
Second step reaction generates two (1,5-cyclo-octadiene) tetrafluoro boric acid rhodium compounds, and described method is divided into following step:
Steps d: silver tetrafluoroborate is dissolved in organic solvent, obtains D solution.
Step e: 1,5-cyclo-octadiene radium chloride dimer is dissolved in organic solvent, and then adds 1,5-cyclo-octadiene, obtain E solution.
Step f: under nitrogen protection, at low temperatures D solution is slowly added drop-wise in E solution to constant temperature stirring reaction one hour.
Step g: the reactant liquor in step f is warmed up to backflow, reacts 12～36 hours. Cold filtration, filtrate, through repeatedly concentrating and separate out solid, is filtered. Merge filter cake, use organic solvent rinsing, solid vacuum drying, obtains two (1,5-cyclo-octadiene) tetrafluoro boric acid rhodium compounds.
The preparation method of above-mentioned rhodium compound, the organic solvent described in step a is methyl alcohol, ethanol, isopropyl alcohol, n-butanol. Rhodium chloride concentration is the solution of 50-150 grams per liter.
The preparation method of above-mentioned rhodium compound, 1 described in step b, the mol ratio of the rhodium chloride described in 5-cyclo-octadiene and step 1 is (6-10): 1, the time of back flow reaction is 12～36 hours.
The preparation method of above-mentioned rhodium compound, the organic solvent described in steps d is oxolane, acetone, carrene.
The preparation method of above-mentioned rhodium compound, 1 described in the silver tetrafluoroborate described in steps d and step e, the dimeric mol ratio of 5-cyclo-octadiene radium chloride is (0.5～1.5): 1, tetrafluoro boric acid silver concentration is the solution of 0.1-0.2 grams per liter.
The preparation method of above-mentioned rhodium compound, 1 described in step e, 5-cyclo-octadiene and the dimeric mol ratio of 1,5-cyclo-octadiene radium chloride are (1～3): 1.
The preparation method of above-mentioned rhodium compound, the cryogenic temperature described in step f is at 15-25 DEG C.
The preparation method of above-mentioned rhodium compound, the reaction temperature described in step g is that 30-50 DEG C of return time is 12-36 hour, its organic solvent is ether, methyl tertiary butyl ether(MTBE), benzinum.
The present invention compared with prior art has following advantage: (1) preparation method of the present invention is simple to operate, and purity is high, and productive rate is high, and product one way total recovery (with metal rhodium) can reach more than 90%, and product purity reaches 99%. (2) production product of the present invention is widely used as catalyst in symmetrical and asymmetric hydrogenation reaction, hydroformylation, hydrosilylation and coupling reaction, presents good catalytic action.
Brief description of the drawings
Fig. 1 is two (1,5-cyclo-octadiene) the tetrafluoro boric acid rhodium compound nucleus magnetic hydrogen spectrum spectrograms of product prepared by method of the present invention.
Detailed description of the invention
Embodiment 1:
10 gram of three rhodium trichloride hydrate is dissolved in 100 milliliters of absolute ethyl alcohols and 20 ml waters, measures 37.4 milliliter 1, and 5-cyclo-octadiene is in constant pressure funnel, and nitrogen replacement protection, starts to drip 1,5-cyclo-octadiene, dropwises and is warming up to 82 DEG C and insulated and stirred 18 hours. Reactant liquor concentrated by rotary evaporation, cold filtration, obtains 1,5-cyclo-octadiene radium chloride dimer. Again above-mentioned solid is all dissolved in 1,5 cyclo-octadiene of the carrene of 240 milliliters and 17.7 milliliters to nitrogen protection; slowly drip at 20 DEG C 60 milliliters of acetone solns that contain 7.5 grams of silver tetrafluoroborates, drip complete 35 DEG C of reactions 24 hours that are warming up to, filter; concentrated by rotary evaporation; filter, use methyl tertiary butyl ether(MTBE) rinsing, vacuum air drying; obtain two 1; 13.8 grams of 5-cyclo-octadiene tetrafluoro boric acid rhodiums, the metal Rh content 24.92% of surveying, theoretical Rh content 25.30%.
Embodiment 2:
100 gram of three rhodium trichloride hydrate is dissolved in 1000 milliliters of absolute ethyl alcohols and 200 ml waters; measure 370 milliliter 1; 5-cyclo-octadiene is in constant pressure funnel, and nitrogen replacement protection, starts to drip 1; 5-cyclo-octadiene; dropwise and be warming up to 82 DEG C and insulated and stirred 24 hours, concentrated by rotary evaporation, cold filtration; obtain 1,5-cyclo-octadiene radium chloride dimer. Again it is all dissolved in to 1 of the carrene of 2400 milliliters and 160 milliliters; in 5 cyclo-octadiene, under nitrogen protection, slowly drip at 20 DEG C 600 milliliters of acetone solns that contain 75 grams of silver tetrafluoroborates; back flow reaction 36 hours at 45 DEG C; filter, concentrated by rotary evaporation, filters; use methyl tertiary butyl ether(MTBE) rinsing; vacuum air drying, obtains 141.05 grams of two 1,5-cyclo-octadiene tetrafluoro boric acid rhodiums. The metal Rh content 24.95% of surveying, theoretical Rh content 25.30%.
Embodiment 3:
100 gram of three rhodium trichloride hydrate is dissolved in 1000 milliliters of absolute ethyl alcohols and 200 ml waters; measure 374 milliliter 1; 5-cyclo-octadiene, in constant pressure funnel, under nitrogen protection, starts to drip 1; 5-cyclo-octadiene; dropwise and be warming up to 82 DEG C and insulated and stirred 24 hours, concentrated by rotary evaporation, filters; obtain 1,5-cyclo-octadiene radium chloride dimer. Again it is all dissolved in to 1 of the carrene of 2000 milliliters and 160 milliliters; in 5 cyclo-octadiene, under nitrogen protection, slowly drip at 20 DEG C 600 milliliters of acetone solns that contain 75 grams of silver tetrafluoroborates; back flow reaction 30 hours at 45 DEG C; filter, concentrated by rotary evaporation, filters; use methyl tertiary butyl ether(MTBE) rinsing; vacuum air drying, obtains 138 grams of two 1,5-cyclo-octadiene tetrafluoro boric acid rhodiums. The metal Rh content 24.90% of surveying, theoretical Rh content 25.30%.
Claims (2)
1. a preparation method for rhodium compound, is characterized in that comprising step:
Step a: three rhodium trichloride hydrates are dissolved in organic solvent and water, and obtaining rhodium chloride concentration is the molten of 50-150 grams per literLiquid.
Step b: under nitrogen protection, 1,5-cyclo-octadiene is added drop-wise in the solution described in step a.
Step c: solution described in step b is warmed to 80 DEG C to refluxing, and then back flow reaction 12-36 hour, filters, and obtains filter cake,Filtrate is concentrated into certain volume and separates out again solid, refilters, and solid vacuum drying obtains 1,5-cyclo-octadiene radium chlorideDimer.
Steps d: silver tetrafluoroborate is dissolved in organic solvent, obtains the solution that tetrafluoro boric acid silver concentration is 0.1-0.2 grams per liter.
Step e: by step c gained 1,5-cyclo-octadiene radium chloride dimer is dissolved in organic solvent, and then add 1,5-ring pungentDiene, obtaining 1,5-cyclo-octadiene radium chloride dimer concentration is the solution of 0,03-0.06 grams per liter.
Step f: under nitrogen protection, at low temperatures steps d kind solution is slowly dripped in step c solution to constant temperature stirring reaction oneIndividual hour.
Step g: solution in step f is warmed to 30-50 DEG C, and back flow reaction 12-36 hour, filters, and filtrate is concentrated, has solidSeparate out, filter, obtain filter cake, filtrate continuation is concentrated into certain volume, separates out again solid, refilters, and finally usesThe agent rinsing of organic Lip river, obtains two (1,5-cyclo-octadiene) tetrafluoro boric acid rhodium compounds.
2. the preparation method of a kind of rhodium compound according to claim 1, is characterized in that:
1) organic solvent described in step a is methyl alcohol, ethanol, isopropyl alcohol, n-butanol. Rhodium chloride concentration is 50-150 grams per literSolution.
2) 1 described in step b, 5-cyclo-octadiene and step: the mol ratio of the rhodium chloride described in a is (6-10): 1.
3) reflux temperature that described in step c, reaction temperature is organic solvent, the time of reaction is 12-36 hour.
4) organic solvent described in steps d is oxolane, acetone, carrene.
5) 1 described in the silver tetrafluoroborate described in steps d and step e, the dimeric mol ratio of 5-cyclo-octadiene radium chloride is(0.5-1.5): 1, tetrafluoro boric acid silver concentration is the solution of 0.1-0.2 grams per liter.
6) 1 described in step e, 1 described in 5-cyclo-octadiene and step e, the dimeric mol ratio of 5-cyclo-octadiene radium chloride is (1-3):1
7) cryogenic temperature described in step f is at 10-25 DEG C.
8) reaction temperature described in step g is 30-50 DEG C, and the reaction time is 12-36 hour, its rinsing organic solvent used be ether,Methyl tertiary butyl ether(MTBE), benzinum.
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| CN110078771A (en) * | 2019-06-06 | 2019-08-02 | 江苏欣诺科催化剂有限公司 | A kind of preparation method of iridium catalyst |
| CN112679554A (en) * | 2020-12-31 | 2021-04-20 | 昆明贵金属研究所 | Preparation of rhodium (I) acid salt [ RhL2]+A-And [ Rh ] andI(CO)2Cl]2method of complexing |
| CN113492021A (en) * | 2021-09-09 | 2021-10-12 | 苏州欣诺科生物科技有限公司 | Preparation method of rhodium catalyst |
| CN113980057A (en) * | 2021-10-26 | 2022-01-28 | 昆明贵金属研究所 | One-pot method for preparing bis (dienylrhodium) (I) nitrate [ RhL [)2]NO3Method of synthesis of |
| CN115057890A (en) * | 2022-06-15 | 2022-09-16 | 浙江微通催化新材料有限公司 | Synthesis method of (1, 5-cyclooctadiene) chlororhodium (I) dimer |
| CN115141233A (en) * | 2022-06-23 | 2022-10-04 | 浙江微通催化新材料有限公司 | Synthesis method of bis (1, 5-cyclooctadiene) rhodium trifluoromethanesulfonate |
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| CN110078771A (en) * | 2019-06-06 | 2019-08-02 | 江苏欣诺科催化剂有限公司 | A kind of preparation method of iridium catalyst |
| CN110078771B (en) * | 2019-06-06 | 2022-04-05 | 江苏欣诺科催化剂有限公司 | Preparation method of iridium catalyst |
| CN112679554A (en) * | 2020-12-31 | 2021-04-20 | 昆明贵金属研究所 | Preparation of rhodium (I) acid salt [ RhL2]+A-And [ Rh ] andI(CO)2Cl]2method of complexing |
| CN112679554B (en) * | 2020-12-31 | 2022-11-29 | 昆明贵金属研究所 | Preparation of rhodium (I) acid salt [ RhL 2 ] + A - And [ Rh ] and I (CO) 2 Cl] 2 method of complexing |
| CN113492021A (en) * | 2021-09-09 | 2021-10-12 | 苏州欣诺科生物科技有限公司 | Preparation method of rhodium catalyst |
| CN113492021B (en) * | 2021-09-09 | 2021-11-19 | 苏州欣诺科生物科技有限公司 | Preparation method of rhodium catalyst |
| CN113980057A (en) * | 2021-10-26 | 2022-01-28 | 昆明贵金属研究所 | One-pot method for preparing bis (dienylrhodium) (I) nitrate [ RhL [)2]NO3Method of synthesis of |
| CN113980057B (en) * | 2021-10-26 | 2023-10-03 | 昆明贵金属研究所 | One-pot method for preparing diene rhodium (I) nitrate [ RhL ] 2 ]NO 3 Is synthesized by the method of (2) |
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| CN115141233A (en) * | 2022-06-23 | 2022-10-04 | 浙江微通催化新材料有限公司 | Synthesis method of bis (1, 5-cyclooctadiene) rhodium trifluoromethanesulfonate |
| CN115141233B (en) * | 2022-06-23 | 2023-12-29 | 浙江微通催化新材料有限公司 | Synthesis method of rhodium bis (1, 5-cyclooctadiene) triflate |
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