CN108774265B - Osmium bidentate diamine complex with catalytic ammonia borane dehydrogenation activity and preparation method thereof - Google Patents
Osmium bidentate diamine complex with catalytic ammonia borane dehydrogenation activity and preparation method thereof Download PDFInfo
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- 150000004985 diamines Chemical class 0.000 title claims abstract description 40
- 229910052762 osmium Inorganic materials 0.000 title claims abstract description 37
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 title abstract description 10
- 230000000694 effects Effects 0.000 title abstract description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 10
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- AXNUJYHFQHQZBE-UHFFFAOYSA-N 3-methylbenzene-1,2-diamine Chemical group CC1=CC=CC(N)=C1N AXNUJYHFQHQZBE-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 150000004987 o-phenylenediamines Chemical class 0.000 claims description 2
- 150000002907 osmium Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000001291 vacuum drying Methods 0.000 claims 1
- MYSMDZQWSJSWHW-UHFFFAOYSA-N azanylidyneosmium Chemical compound [Os]#N MYSMDZQWSJSWHW-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000000243 solution Substances 0.000 description 12
- 239000012043 crude product Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 4
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 3
- 241000272814 Anser sp. Species 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VPMJBJSLTPBZLR-UHFFFAOYSA-N 3,6-dibromobenzene-1,2-diamine Chemical compound NC1=C(N)C(Br)=CC=C1Br VPMJBJSLTPBZLR-UHFFFAOYSA-N 0.000 description 1
- VWYTZNPMXYCBPK-UHFFFAOYSA-N 3-bromobenzene-1,2-diamine Chemical compound NC1=CC=CC(Br)=C1N VWYTZNPMXYCBPK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- 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
- C07F15/002—Osmium compounds
- C07F15/0026—Osmium compounds without a metal-carbon linkage
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/825—Osmium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
Abstract
The invention discloses an osmium bidentate diamine complex with catalytic ammonia borane dehydrogenation activity and a preparation method thereof, belonging to the technical field of inorganic synthesis and catalysis. Adding OsCl2(PPh3)3The osmium-nitrogen complex can be reacted with o-phenylenediamine bidentate diamine active ligand in an organic solvent at room temperature to generate a series of osmium-nitrogen complexes. When the catalyst is applied to the catalytic ammonia borane dehydrogenation reaction, the catalyst has high catalytic reaction activity.
Description
Technical Field
The invention relates to an osmium bidentate diamine complex with catalytic ammonia borane dehydrogenation activity and a preparation method thereof, belonging to the technical field of inorganic synthesis and catalysis.
Background
In recent years, with the increasing energy and environmental problems, the development of sustainable clean energy systems to replace the existing energy carriers is urgent. The hydrogen energy becomes the first-choice novel energy source with a plurality of advantages of large reserve, wide distribution, high combustion value, zero pollution to the environment and the like. However, a safe and efficient hydrogen storage and transportation method is the key to the large-scale application of hydrogen energy. Chemical hydrogen storage has the advantages of high hydrogen storage density, good safety and the like, and has attracted wide attention in recent years. Wherein ammonia borane (NH)3BH3AB) a solid that is stable at room temperature by virtue of its theoretical hydrogen storage capacity of up to 19.6 wt% is the most potential chemical hydrogen storage material.
However, ammonia borane has various advantages as a potential hydrogen storage material, but still has the problems of high hydrogen release temperature in the hydrogen release process, impurity gas generation, volume expansion, difficult regeneration and the like in the hydrogen release process. For this reason, a series of studies for improving the hydrogen release performance of ammonia borane are rapidly spreading worldwide, such as supporting ammonia borane on porous materials, metal substitution chemical activation, using additives or catalysts, and the like. Among the many measures, the dehydrogenation of ammonia borane by metal catalysis is one of the most effective methods for improving the amount of hydrogen release, the selectivity and the kinetics of the hydrogen release reaction.
Currently, ammonia borane dehydrogenation catalysts that have been studied internationally involve a variety of metals in the early, intermediate and late transition series [ chem. rev.2010,110,4023-4078 ]. Among them, three transition metal catalysts of ruthenium, rhodium and iridium have exhibited relatively excellent performance [ Synthesis and Application of organic compounds. topics in organic chemical chemistry.2015,49, 153. 220 ], and their introduction has changed reaction path, reduced reaction activation energy, effectively increased hydrogen release reaction rate and reduced hydrogen release temperature. The third transition metal osmium, ruthenium, rhodium and iridium are in the VIII group of the periodic table of elements, and have certain similarity in properties, and the latter three are widely applied to the catalytic ammonia borane dehydrogenation reaction, so that the osmium metal has great possibility of being applied to the reaction and is expected to become a novel ammonia borane dehydrogenation catalyst.
Therefore, the development of new, highly efficient osmium catalysts with catalytic ammonia borane dehydrogenation activity is worthy of further exploration and development.
Disclosure of Invention
The invention solves the technical problem of providing a novel osmium bidentate diamine complex catalyst and a preparation method thereof, and the novel osmium bidentate diamine complex catalyst with high efficiency for catalyzing ammonia borane dehydrogenation is prepared by selecting a proper active diamine ligand and designing and optimizing a synthetic route.
The method for preparing the osmium bidentate diamine complex is characterized by comprising the following steps: adding OsCl2(PPh3)3Reacting with active bidentate diamine in an organic solvent to obtain the osmium bidentate diamine complex.
The osmium bidentate diamine complex has the following structure:
further, in the above technical solution, the bidentate N ligand is selected from o-phenylenediamine or substituted o-phenylenediamine, preferably,
further, in the above technical scheme, the reaction is carried out under anhydrous and oxygen-free conditions.
Further, in the above technical solution, the OsCl2(PPh3)3The molar ratio to the active bidentate N ligand is 1:1-2, preferably 1:1.2, and the reaction temperature is between 20 and 25 ℃.
Further, in the above technical solution, the reaction solvent is selected from dichloromethane, chloroform, tetrahydrofuran or 1, 2-dichloroethane. Dichloromethane solvents are preferred.
The specific reaction steps comprise:
(1) preparation of crude osmium bidentate diamine complex: adding OsCl into a reaction bottle2(PPh3)3Adding an anhydrous solvent to dissolve the mixture and a bidentate diamine ligand, stirring the mixture to react, and concentrating the mixture under reduced pressure to obtain a crude osmium bidentate diamine complex;
(2) purification of crude osmium bidentate diamine complex: washing the crude product by using an anhydrous solvent, filtering and drying to obtain a purified osmium bidentate diamine complex solid;
OsCl in step (1)2(PPh3)3The molar ratio of the bidentate diamine ligand to the bidentate diamine ligand is 1:1-2, and the reaction condition is that the mixture is stirred for 1-10h at the temperature of 15-30 ℃. The preferable reaction condition is that the mixture is stirred for 1.5 to 2 hours at the temperature of between 20 and 25 ℃;
the organic solvent washing solvent in the step (2) is selected from n-pentane, n-hexane or n-heptane. The preferred solvent is n-hexane, and the number of washing times is preferably 4.
Preferably, the drying in the step (2) is carried out by adopting vacuum/high-purity nitrogen flow switching, and the switching frequency is 0.5-1 h/time;
in the present invention, the high-purity nitrogen gas used in the drying is a nitrogen gas having a purity of 99.95% to 99.99%.
The invention has the beneficial effects that:
the preparation method of the osmium bidentate diamine complex has the advantages of simple steps, mild reaction conditions and low energy consumption, and is suitable for large-scale production. The obtained complex shows excellent catalytic activity in catalyzing ammonia borane dehydrogenation reaction.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
O-phenylenediamine (22mg,0.20mmol) and OsCl were weighed out2(PPh3)3(178mg,0.17mmol) was charged into a 25mL magneton reaction flask under N2Under protection, 15mL of dichloromethane solvent is added, the mixture is stirred and reacts for 2 hours at the temperature of 20-25 ℃, and the solution is changed into brownish red from dark green. After the reaction is finished, concentrating the reaction solution, and adding 20mL of anhydrous n-hexane to form a goose yellow precipitate, namely the o-phenylenediamine-substituted osmium nitrogen complex crude product. And washing the crude product by using normal hexane (4 times, 40mL), filtering and drying to obtain the purified osmium nitrogen complex, namely a goose yellow solid with the yield of 136mg and the yield of 90%.
The result of the nuclear magnetic resonance analysis was1H NMR(600MHz,CDCl3)δ：7.4(broad s,12H,PPh3),7.2(t,J＝7.2Hz,6H,PPh3),7.1(t,J＝7.2Hz,12H,PPh3),7.0(broad s,2H,Ar),6.8(broad s,2H,Ar),5.0(broad s,4H,NH2).13C{1H}NMR(151MHz,CDCl3)δ：140.3(s,Ar),138.0(d,J＝7.4Hz,Ar),137.5(d,J＝7.7Hz,Ar),134.6(t,J＝7.0Hz,PPh3),128.9(s,PPh3),127.6(s,PPh3),127.4(t,J＝7.8Hz,PPh3).31P{1H}NMR(162MHz,CDCl3)δ：-12.7(s,PPh3).
Elemental analysis (%) theoretical value (OsC)42H38N2P2Cl2) C, 56.44; h, 4.29; n,3.13, found: c, 56.75; h, 4.31; and N,3.04.
Example 2
3-methyl-o-phenylenediamine (24mg,0.20mmol) and OsCl were weighed2(PPh3)3(178mg,0.17mmol) 25mL of a catalyst containing magnetonsIn a reaction flask, in N2Under protection, 15mL of dichloromethane solvent is added, the mixture is stirred and reacts for 2 hours at the temperature of 20-25 ℃, and the solution is changed into brownish red from dark green. After the reaction is finished, concentrating the reaction solution, and adding 20mL of anhydrous n-hexane to form yellow precipitate, namely the crude product of the 3-methyl-o-phenylenediamine-substituted osmium nitrogen complex. And washing the crude product by using normal hexane (4 times, 40mL), filtering and drying to obtain a purified osmium nitrogen complex yellow solid with the yield of 133mg and the yield of 86%.
The result of the nuclear magnetic resonance analysis was1H NMR(600MHz,CDCl3)δ:7.5(q,J＝8.8Hz,12H,PPh3),7.2(t,J＝4.4Hz,6H,PPh3),7.1(t,J＝7.5Hz,12H,PPh3),6.9(t,J＝7.5Hz,1H,Ar),6.8(d,J＝3.6Hz,1H,Ar),6.6(d,J＝4.5Hz,1H,Ar),5.0(broad s,2H,NH2),4.7(broad s,2H,NH2),1.8(s,3H,CH3).13C{1H}NMR(151MHz,CDCl3)δ:139.3(s,Ar),138.2(s,Ar),137.0(s,Ar),136.8(s,Ar),136.7(s,Ar),136.5(s,Ar),134.6(s,Ar),133.7～133.5(m,PPh3),133.0(s,Ar),128.6(s,Ar),127.8(s,PPh3),126.6(s,Ar),126.5(s,Ar),126.4～126.3(m,PPh3),124.2(s,Ar),16.0(s,CH3).31P{1H}NMR(243MHz,CDCl3)δ:-12.0(s,PPh3),-12.7(s,PPh3).
Elemental analysis (%) theoretical value (OsC)43H40N2P2Cl2) C, 56.89; h, 4.44; n,3.09 observed values are: c, 57.01; h, 4.34; and N,3.10.
Example 3
3-bromo-o-phenylenediamine (38mg,0.2mmol) and OsCl were weighed2(PPh3)3(178mg,0.17mmol) was charged into a 25mL magneton reaction flask under N2Under protection, 15mL of dichloromethane solvent is added, the mixture is stirred and reacts for 2 hours at the temperature of 20-25 ℃, and the solution is changed into brownish red from dark green. After the reaction is finished, concentrating the reaction solution, and adding 20mL of anhydrous n-hexane to form yellow precipitate, namely the crude product of the 3-bromo-o-phenylenediamine-substituted osmium nitrogen complex. Washing the crude product with n-hexane (4 times, 40mL), filtering, and drying to obtain purified osmium nitrogen complex yellow solidYield 129mg, 78%.
The result of the nuclear magnetic resonance analysis was1H NMR(600MHz,CDCl3)δ:7.4(broad s,12H,PPh3),7.3(broad s,1H,Ar),7.2(broad s,PPh3),7.1(broad s,12H,PPh3),6.9(t,J＝6.3Hz,1H,Ar),6.8(d,J＝7.2Hz,1H,Ar),5.1(broad s,2H,NH2),4.9(broad s,2H,NH2).13C{1H}NMR(151MHz,CDCl3)δ:141.2(s,Ar),139.6(s,Ar),136.8(s,Ar),136.6(s,Ar),136.5(s,Ar),136.2(s,Ar),133.5(d,J＝9.0Hz,,PPh3),132.9(s,Ar),130.1(s,Ar),128.7(s,Ar),127.9(d,J＝3.0Hz,PPh3),126.8(s,Ar),126.5(d,J＝9.0Hz,PPh3),126.4(d,J＝9.0Hz,PPh3),126.0(s,Ar),122.6(s,Ar).31P{1H}NMR(243MHz,CDCl3)δ:-12.7(s,PPh3),-13.1(s,PPh3).
Elemental analysis (%) theoretical value (OsC)42H37N2P2Cl2Br) C, 51.86; h, 3.83; n,2.88. found: c, 51.99; h, 3.99; n,2.51.
Example 4
3, 6-dibromo-1, 2-phenylenediamine (54mg,0.2mmol) and OsCl were weighed2(PPh3)3(178mg,0.17mmol) was charged into a 25mL magneton reaction flask under N2Under protection, 15mL of dichloromethane solvent is added, the mixture is stirred and reacts for 1.5h at the temperature of 20-25 ℃, and the solution is changed into brownish red from dark green. After the reaction is finished, concentrating the reaction solution, and adding 20mL of anhydrous n-hexane to form yellow precipitate, namely the crude product of the 3, 6-dibromo-o-phenylenediamine-substituted osmium nitrogen complex. And washing the crude product by using normal hexane (4 times, 40mL), filtering and drying to obtain the purified osmium nitrogen complex yellow solid with the yield of 161mg and the yield of 90%.
The result of the nuclear magnetic resonance analysis was1H NMR(600MHz,CDCl3)δ:7.5(t,J＝8.1Hz,12H,PPh3),7.2(t,J＝6.3Hz,6H,PPh3),7.1(t,J＝7.5Hz,12H,PPh3),7.1(s,2H,Ar),5.0(s,4H,NH2).13C{1H}NMR(151MHz,CDCl3)δ:141.3(s,Ar),133.6(s,PPh3),131.1(s,Ar),128.2(s,PPh3),126.4(broad s,PPh3),121.9(s,Ar).31P{1H}NMR(243MHz,CDCl3)δ:-13.1(s,PPh3).
Elemental analysis (%) theoretical value (OsC)42H36N2P2Cl2Br2) C, 47.97; h, 3.45; n,2..66. found: c, 48.12; h, 3.81; n,2.31.
Example 5
Test for catalytic Performance
Using the osmium bidentate diamine complexes prepared in examples 1 to 4 as catalysts, a dry 25mL Schlenk flask was charged with a solution of ammonia borane (1.77mmol) in tetrahydrofuran (5mL) and an osmium bidentate diamine complex catalyst (0.09mmol) in ethylene glycol dimethyl ether (8mL) under anhydrous and oxygen-free conditions, and the side ports of the Schlenk flask were closed after mixing. The side branch was then connected to a plastic tube attached to a burette for measuring gas, and the Schlenk bottle was transferred to a 60 ℃ oil bath, the magneton speed was controlled at 300rpm, the branch and stopwatch were opened, hydrogen gas was collected and the time was recorded. The volume of hydrogen was recorded at different time intervals.
The osmium bidentate diamine complex catalyst prepared in the examples 1 to 4 catalyzes ammonia borane to release hydrogen at 60 ℃ in a tetrahydrofuran/ethylene glycol dimethyl ether mixed solution (volume ratio is 1:1.6) when the catalyst loading is 5 mol%, and the test results show that the synthesized osmium bidentate diamine complex has good catalytic activity when used as the catalyst, so that the ammonia borane can release 1.88 to 2.29 equivalents of H2. Wherein, the 3-methyl-o-phenylenediamine substituted osmium bidentate diamine complex catalyst in the example 2 has the highest activity, and the TOF value reaches 200h-1Is currently the most efficient osmium catalyst. The osmium bidentate diamine complex has potential application as an efficient osmium catalyst for ammonia borane dehydrogenation.
aMeasured in terms of the time required to release 1 equivalent of hydrogen,
TABLE 1 examples 1-4 preparation of osmium bidentate diamine complexes to catalyze the dehydrogenation of ammonia borane
The foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (9)
1. An osmium bidentate diamine complex catalyst is characterized by having the following chemical structure:
2. a process for preparing an osmium bidentate diamine complex according to claim 1, characterized in that it comprises the following operations: OsCl2(PPh3)3Reacting with bidentate diamine ligand in a solvent to obtain the complex.
3. A process for preparing an osmium bidentate diamine complex according to claim 2, wherein: the bidentate diamine ligand is selected from o-phenylenediamine or substituted o-phenylenediamine.
4. A process for preparing an osmium bidentate diamine complex according to claim 2, wherein: the reaction solvent is selected from dichloromethane, chloroform, tetrahydrofuran or 1, 2-dichloroethane.
5. A process for preparing an osmium bidentate diamine complex according to claim 2, wherein: the reaction is carried out under the anhydrous and oxygen-free conditions, and the reaction temperature is 20-25 ℃.
6. A process for preparing an osmium bidentate diamine complex according to claim 2, wherein: the OsCl2(PPh3)3The molar ratio to bidentate diamine ligand is 1: 1-2.
7. A process for the preparation of an osmium bidentate diamine complex according to any of claims 2 to 6, characterized in that: the complex is washed by anhydrous solvent and purified after vacuum drying; the washing solvent is selected from n-pentane, n-hexane or n-heptane.
8. The use of the osmium bidentate diamine complex according to claim 1 to catalyze the dehydrogenation of ammonia borane, wherein: the osmium bidentate diamine complex is used for catalyzing ammonia borane dehydrogenation reaction.
9. The use of the osmium bidentate diamine complex according to claim 8 in catalyzing the dehydrogenation of ammonia borane, wherein: the 3-methyl o-phenylenediamine substituted osmium complex is used for catalyzing ammonia borane dehydrogenation reaction.
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| CN105833914A (en) * | 2016-04-13 | 2016-08-10 | 大连理工大学 | Dinuclear complex catalyst, preparation method and application thereof in preparing hydrogen by catalyzing formic acid decomposition |
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| CN105833914A (en) * | 2016-04-13 | 2016-08-10 | 大连理工大学 | Dinuclear complex catalyst, preparation method and application thereof in preparing hydrogen by catalyzing formic acid decomposition |
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| Chemistry of osmium in N2P2Br2 coordination sphere Synthesis, structure and reactivities;Anindya Das等;《Polyhedron》;19990921;第18卷;第2729-2736页 * |
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