CN104045668B - Ferrocene tetrazole metal complex and preparation method thereof - Google Patents
Ferrocene tetrazole metal complex and preparation method thereof Download PDFInfo
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- -1 Ferrocene tetrazole metal complex Chemical class 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 150000001450 anions Chemical class 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 229960004756 ethanol Drugs 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 13
- 150000003536 tetrazoles Chemical group 0.000 abstract description 10
- 238000002485 combustion reaction Methods 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 239000003380 propellant Substances 0.000 abstract description 7
- 239000004449 solid propellant Substances 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 28
- 238000000034 method Methods 0.000 description 12
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 150000004696 coordination complex Chemical class 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 10
- 150000001455 metallic ions Chemical class 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 244000061458 Solanum melongena Species 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LNDKRVOOYMEYTC-UHFFFAOYSA-N buta-1,3-dien-1-ol Chemical compound OC=CC=C LNDKRVOOYMEYTC-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
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- 229920000578 graft copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 235000019515 salmon Nutrition 0.000 description 1
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- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The invention discloses a kind of ferrocene tetrazole metal complex and preparation method thereof, this coordination compound is with Mn2+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+Or Pb2+Centered by metal ion, with the ferrocene tetrazole containing ferrocene group and high azacyclo-tetrazole group for anion, tetrazole group can improve the energy level of propellant when thermal decomposition, synergism between metal ion and ferrocene group can improve the combustion catalysis effect of ferrocene burningrate catalyst, it is simultaneously introduced assistant ligand and increases the heat stability of coordination compound, and regulate and control the combustion catalysis performance of coordination compound. The ferrocene tetrazole metal complex Heat stability is good of the present invention, generation heat and the combustion heat are high, for, in solid propellant, solid propellant being contributed energy while catalysis. The preparation method of ferrocene tetrazole metal complex of the present invention is simple, need not heat and can synthesize in air atmosphere, and synthesis cost is low, and products collection efficiency is high, it is possible to suitable in commercial application.
Description
Technical field
The invention belongs to the synthesis technical field of combustionregulator in solid propellant propulsion agent prescription, be specifically related to a kind of ferrocene tetrazole metal complex and preparation method thereof.
Background technology
Ferrocene and its derivative; burning regulatory function because of its excellence; topmost combustion speed (burning) catalyst as solid propellant (especially composite propellant); it is widely used in strategy, Tactical Weapon System, in the weapons such as various ballistic missiles (including region of war, short distance, intermediate range, intercontinental ballistic missile etc.), airborne tactical missile, anti-ballistic high-speed circuit design and sea base submarine mine, torpedo, has played huge effect.
The problems such as the ferrocene class combustionregulator owing to applying at present easily migrates, volatile, low temperature crystallization are solved not yet at all, have a strong impact on the storage life of all kinds of missile propellant powder charge of China, dependability and environmental suitability, also virtually significantly increase the funds expenditure of national defence basis deposit. So researcheres have done substantial amounts of research work to improving these problems that Ferrocene and its derivative exists. One of method more common at present is to be connected on the side chain of macromole or main chain to form the polymer containing ferrocene by ferrocene group. The Butacene that explosive wastewater association of France develops is exactly ferrocene derivatives and low molecular weight hydroxy-terminated polybutadiene graft copolymer, when preparing propellant, it can common adhesive (such as end hydroxy butadiene (HTPB)) in part alternative composite propellant, in propellant curing process, it can enter curing network, but this analog derivative manufacturing process is complicated, oxidant is sensitive, iron content is few, catalytic efficiency is not high, and the existence of ferrum can cause fourth hydroxyl binding agent degradation reaction in depositing process, reduce the performance of fourth hydroxyl binding agent.Li Feng life in 2008 et al. report in " solid-rocket technology " the 30th volume the 6th phase 612～616 pages (2008) is grafted to ferrocene on SBA-15 by condensation reaction, is prepared for the catalyst of a kind of low migration. But this catalyst iron-holder is low, and introducing the Si oxide without energy, catalytic effect neither be fine. In addition, people introduce epoxy ethyl, sulfydryl, azepine base etc. in ferrocene-containing compound and are prone to the active function groups of polymerization, by these compounds testing in solid propellant is found that they can partly solve the problem migrated, but all cannot obtain the perfect combination of mechanical property, processing performance and combustibility.
Summary of the invention
The deficiency that the technical problem to be solved is in that to overcome in prior art existing for ferrocene derivatives, a kind of not volatile, Heat stability is good under field conditions (factors) is provided, there is the higher ferrocene tetrazole metal complex generating heat and the combustion heat, and provide a kind of preparation method for this coordination compound.
Solve above-mentioned technical problem and be the technical scheme is that the formula of this coordination compound is [Ma(L1)b(L2)c](L3)dN (sol),
In above-mentioned formula, M is Mn2+Time, L1For 2,2-bipyridyl or 1,10-Phen, L2For H2O、L3For ferrocene tetrazole univalent anion, wherein L1When being 2,2-bipyridyl, a=1, b=1, c=4, d=2, n=0, L1When being 1,10-Phen, a=1, b=2, c=2, d=2, n=0.
In above-mentioned formula, M is Co2+Time, L1For 1,10-Phen, L3For the H that ferrocene tetrazole univalent anion, sol are free2O molecule, a=1, b=3, c=0, d=2, n=7.
In above-mentioned formula, M is Ni2+Time, L1For 1,10-Phen, L3For the H that ferrocene tetrazole univalent anion, sol are free2O molecule, a=1, b=3, c=0, d=2, n=9.
In above-mentioned formula, M is Cu2+Time, L1For 2,2-bipyridyl, L2It is free ethanol molecule, a=2, b=2, c=4, d=0, n=1 for ferrocene tetrazole univalent anion, sol, or L1For 1,10-Phen, L3For the H that ferrocene tetrazole univalent anion, sol are free2O molecule, a=1, b=3, c=0, d=2, n=8.
In above-mentioned formula, M is Zn2+Time, L1For 1,10-Phen, L3For the H that ferrocene tetrazole univalent anion, sol are free2O molecule, a=1, b=3, c=0, d=2, n=7.
In above-mentioned formula, M is Cd2+Time, L1For 2,2-bipyridyl, L2For ferrocene tetrazole univalent anion, a=1, b=2, c=2, d=0, n=0, or L1For 1,10-Phen, L2For H2O、L3For ferrocene tetrazole univalent anion, a=1, b=2, c=2, d=2, n=0.
In above-mentioned formula, M is Pb2+Time, L1For 1,10-Phen, L2For CO3 2-、L3It is free 1,10-Phen molecule, a=2, b=4, c=1, d=2, n=1 for ferrocene tetrazole univalent anion, sol.
The preparation method of above-mentioned ferrocene tetrazole metal complex is: be dissolved completely in distilled water by water-soluble metal salt, it is subsequently adding and is dissolved completely in the 1 of dehydrated alcohol, 10-Phen or 2, 2-bipyridyl solution, stir, add the ferrocene tetrazole sodium salt solution being dissolved completely in distilled water, water-soluble metal salt, 1, 10-Phen or 2, 2-bipyridyl, the mol ratio of ferrocene tetrazole sodium salt is 1:2:2, stir 20～30 minutes, filter, filtrate is stood to forming crystal under the dustless condition of room temperature, namely ferrocene tetrazole metal complex is obtained.
Above-mentioned water-soluble metal salt is Mn2+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+、Pb2+In any one villaumite, acetate or sulfate.
The present invention constructs the ferrocene tetrazole metal complex of different structure by different assistant ligands, this coordination compound not only contains the ferrocene group required by ferrocene class catalyst, and containing this high nitrogen heterocycle perssad with the positive enthalpy of formation of tetrazole, can improve the energy level of propellant when thermal decomposition, the synergism between metal ion and ferrocene group can improve the combustion catalysis effect of ferrocene burningrate catalyst simultaneously. It addition, the introducing of assistant ligand can increase the heat stability of coordination compound, and regulate and control the combustion catalysis performance of coordination compound.
The ferrocene tetrazole metal complex Heat stability is good of the present invention, generation heat and the combustion heat are high, for, in solid propellant, solid propellant being contributed energy while catalysis. And the preparation method of coordination compound of the present invention is simple, need not heat and can synthesize in air atmosphere, synthesis cost is low, and products collection efficiency is high, overcomes that Ferrocene and its derivative synthesis technique is complicated, high in cost of production shortcoming, it is possible to suitable in commercial application. The present invention obtains the research fund of project of national nature science fund project (21171112).
Accompanying drawing explanation
Fig. 1 is the coordination environment figure of the ferrocene tetrazole bipyridyl manganese salt of embodiment 1 preparation.
Fig. 2 is the coordination environment figure of the ferrocene tetrazole Phen manganese salt of embodiment 2 preparation.
Fig. 3 is the coordination environment figure of the ferrocene tetrazole Phen cobalt salt of embodiment 3 preparation.
Fig. 4 is the coordination environment figure of the ferrocene tetrazole Phen nickel salt of embodiment 4 preparation.
Fig. 5 is the coordination environment figure of the ferrocene tetrazole bipyridyl mantoquita of embodiment 5 preparation.
Fig. 6 is the coordination environment figure of the ferrocene tetrazole Phen mantoquita of embodiment 6 preparation.
Fig. 7 is the coordination environment figure of the ferrocene tetrazole Phen zinc salt of embodiment 7 preparation.
Fig. 8 is the coordination environment figure of the ferrocene tetrazole bipyridyl cadmium salt of embodiment 8 preparation.
Fig. 9 is the coordination environment figure of the ferrocene tetrazole Phen cadmium salt of embodiment 9 preparation.
Figure 10 is the coordination environment figure of the ferrocene tetrazole Phen lead salt of embodiment 10 preparation.
Figure 11 is the differential scanning calorimetric analysis curve of embodiment 1～10 coordination compound in ammonium perchlorate.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in more detail, but protection scope of the present invention is not limited only to these embodiments.
Ferrocene tetrazole sodium salt in example below is to synthesize according to literature method, method particularly includes: being dissolved completely in ethanol by ferrocene tetrazole, then be added dropwise over sodium hydrate aqueous solution, backflow, with being covered with Al2O3Sand core funnel sucking filtration, obtain settled solution, be spin-dried for, obtain orange/yellow solid and ferrocene tetrazole sodium salt.
Embodiment 1
To prepare ferrocene tetrazole bipyridyl manganese salt, its formula is [Ma(L1)b(L2)c](L3)dN (sol), in formula, M is Mn2+、L1For 2,2-bipyridyl, L2For H2O、L3For ferrocene tetrazole univalent anion, a=1, b=1, c=4, d=2, n=0, preparation method is as follows:
By 19.97mg (0.1mmol) MnCl2·4H2O is dissolved completely in 15mL distilled water, treat solution clear, it is subsequently adding the 31.23mg (0.2mmol) 2 being dissolved completely in 15mL dehydrated alcohol, 2-bipyridyl, stir 10 minutes, obtain yellow solution, in yellow solution, it is added dropwise over being dissolved completely in 55.2mg (0.2mmol) the ferrocene tetrazole sodium salt of 15mL distilled water again, orange colour flocculent deposit is had to generate immediately, filter, filtrate being stood 7 days under the dustless condition of room temperature, obtain orange crystals ferrocene tetrazole bipyridyl manganese salt, calculating its productivity according to Mn is 56%.
The mono-crystalline structures of prepared ferrocene tetrazole bipyridyl manganese salt is shown in Fig. 1, belongs to monoclinic system, P2 (1)/c space group, and cell parameter a isB isC isα is 90 °, β is 102.249 (2) °, γ is 90 °. The separate unit of this metal complex exists independent Mn (II) ion, a neutrality 2,2-bipyridyl molecule and four hydrones, wherein 2,2-bipyridyl and hydrone and central metallic ions effect participate in coordination, and two other ferrocene tetrazole univalent anion is free in coordination compound lattice as counter anion. Prepared product elemental analysis, theoretical value: C48.69%, H4.34%, N17.75%; Experiment value: C47.14%, H4.09%, N16.94%.
Embodiment 2
To prepare ferrocene tetrazole Phen manganese salt, its formula is [Ma(L1)b(L2)c](L3)dN (sol), in formula, M is Mn2+、L1For 1,10-Phen, L2For H2O、L3For ferrocene tetrazole univalent anion, a=1, b=2, c=2, d=2, n=0, preparation method is as follows:
In embodiment 1,2,2-bipyridyls used are with equimolar 1,10-Phen is replaced, and other steps are identical with embodiment 1, and filtrate stands 1 day under the dustless condition of room temperature, obtaining orange crystals ferrocene tetrazole Phen manganese salt, calculating its productivity according to Mn is 78%.
The mono-crystalline structures of prepared ferrocene tetrazole Phen manganese salt is shown in Fig. 2, belongs to monoclinic system, P2 (1)/c space group, and cell parameter a isB isC isα is 90 °, β is 95.234 (2) °, γ is 90 °. The separate unit of this metal complex exists independent Mn (II) ion, two neutrality 1,10-Phen molecule and two hydrones, wherein 1,10-Phen and hydrone and central metallic ions effect participate in coordination, and two other ferrocene tetrazole univalent anion is free in coordination compound lattice as counter anion. Prepared product elemental analysis, theoretical value: C59.96%, H3.28%, N15.20%; Experiment value: C58.61%, H3.54%, N14.48%.
Embodiment 3
To prepare ferrocene tetrazole Phen cobalt salt, its formula is [Ma(L1)b(L2)c](L3)dN (sol), in formula, M is Co2+、L1For 1,10-Phen, L3For the H that ferrocene tetrazole univalent anion, sol are free2O molecule, a=1, b=3, c=0, d=2, n=7, preparation method is as follows:
In example 2, MnCl used2·4H2O is with equimolar Co (CH3COO)2Replacing, other steps are identical with embodiment 2, and filtrate stands 7 days under the dustless condition of room temperature, obtains salmon pink crystal ferrocene tetrazole Phen cobalt salt, and calculating its productivity according to Co is 47%.
The mono-crystalline structures of prepared ferrocene tetrazole Phen cobalt salt is shown in Fig. 3, belongs to anorthic system, P-1 space group, and cell parameter a isB isC isα is 97.811 (2) °, β is 98.258 (2) °, γ is 109.420 (3) °. The separate unit of this metal complex exists independent Co (II) ion, three neutrality 1,10-Phen molecule, wherein 1,10-Phen participates in coordination with central metallic ions effect, and two other ferrocene tetrazole univalent anion is free in coordination compound lattice as counter anion. Prepared product elemental analysis, theoretical value: C56.74%, H4.27%, N15.97%; Experiment value: C55.61%, H5.13%, N14.92%.
Embodiment 4
To prepare ferrocene tetrazole Phen nickel salt, its formula is [Ma(L1)b(L2)c](L3)dN (sol), in formula, M is Ni2+、L1For 1,10-Phen, L3For the H that ferrocene tetrazole univalent anion, sol are free2O molecule, a=1, b=3, c=0, d=2, n=9, preparation method is as follows:
In example 2, MnCl used2·4H2The equimolar NiSO of O4·7H2O replaces, and other steps are identical with embodiment 2, and filtrate stands two weeks under the dustless condition of room temperature, obtains aubergine crystal ferrocene tetrazole Phen nickel salt, and calculating its productivity according to Ni is 39%.
The mono-crystalline structures of prepared ferrocene tetrazole Phen nickel salt is shown in Fig. 4, belongs to anorthic system, P-1 space group, and cell parameter a isB isC isα is 97.897 (2) °, β is 98.566 (2) °, γ is 109.431 (2) °. The separate unit of this metal complex exists independent Ni (II) ion, three neutrality 1,10-Phen molecule, wherein 1,10-Phen participates in coordination with central metallic ions effect, and two other ferrocene tetrazole univalent anion is free in coordination compound lattice as counter anion. Prepared product elemental analysis, theoretical value: C54.96%, H4.77%, N15.47%; Experiment value: C54.08%, H5.13%, N14.96%.
Embodiment 5
To prepare ferrocene tetrazole bipyridyl mantoquita, its formula is [Ma(L1)b(L2)c](L3)dN (sol), in formula, M is Cu2+、L1For 2,2-bipyridyl, L2Being free ethanol molecule, a=2, b=2, c=4, d=0, n=1 for ferrocene tetrazole univalent anion, sol, preparation method is as follows:
In embodiment 1, MnCl used2·4H2The equimolar CuSO of O4·5H2O replaces, and other steps are identical with embodiment 1, and filtrate stands 10 days under the dustless condition of room temperature, obtains blackish green crystal ferrocene tetrazole bipyridyl mantoquita, and calculating its productivity according to Cu is 79%.
The mono-crystalline structures of prepared ferrocene tetrazole bipyridyl mantoquita is shown in Fig. 5, belongs to orthorhombic system, P-1 space group, and cell parameter a isB isC isα is 90 °, β is 90 °, γ is 90 °. The separate unit of this metal complex exists two independent Cu (II) ions, two neutrality 2,2-bipyridyl molecule, four ferrocene tetrazole univalent anions, wherein 2,2-bipyridyls and ferrocene tetrazole univalent anion participate in coordination with central metallic ions effect. Prepared product elemental analysis, theoretical value: C52.93%, H3.90%, N18.70%; Experiment value: C52.11%, H4.32%, N18.27%.
Embodiment 6
To prepare ferrocene tetrazole Phen mantoquita, its formula is [Ma(L1)b(L2)c](L3)dN (sol), in formula, M is Cu2+、L1For 1,10-Phen, L3For the H that ferrocene tetrazole univalent anion, sol are free2O molecule, a=1, b=3, c=0, d=2, n=8, preparation method is as follows:
In embodiment 5,2,2-bipyridyls used are with equimolar 1,10-Phen is replaced, and other steps are identical with embodiment 5, and filtrate stands 7 days under the dustless condition of room temperature, obtaining aubergine crystal ferrocene tetrazole Phen mantoquita, calculating its productivity according to Cu is 75%.
The mono-crystalline structures of prepared ferrocene tetrazole Phen mantoquita is shown in Fig. 6, belongs to anorthic system, P-1 space group, and cell parameter a isB isC isα is 98.248 (2) °, β is 97.876 (2) °, γ is 109.583 (2) °. The separate unit of this metal complex exists independent Cu (II) ion, three neutrality 1,10-Phen molecule, wherein 1,10-Phen participates in coordination with central metallic ions effect, and two other ferrocene tetrazole univalent anion is free in coordination compound lattice as counter anion. Prepared product elemental analysis, theoretical value: C55.53%, H4.66%, N15.63%; Experiment value: C55.11%, H4.98%, N15.12%.
Embodiment 7
To prepare ferrocene tetrazole Phen zinc salt, its formula is [Ma(L1)b(L2)c](L3)dN (sol), in formula, M is Zn2+、L1For 1,10-Phen, L3For the H that ferrocene tetrazole univalent anion, sol are free2O molecule, a=1, b=3, c=0, d=2, n=7, preparation method is as follows:
In example 2, MnCl used2·4H2The equimolar ZnSO of O4·7H2O replaces, and other steps are identical with embodiment 2, and filtrate stands 30 days under the dustless condition of room temperature, obtains shiny red crystal ferrocene tetrazole Phen zinc salt, and calculating its productivity according to Zn is 81%.
The mono-crystalline structures of prepared ferrocene tetrazole Phen zinc salt is shown in Fig. 7, belongs to anorthic system, P-1 space group, and cell parameter a isB isC isα is 97.942 (2) °, β is 98.722 (2) °, γ is 109.062 (3) °. The separate unit of this metal complex exists independent Zn (II) ion, three neutrality 1,10-Phen molecule, wherein 1,10-Phen participates in coordination with central metallic ions effect, and two other ferrocene tetrazole univalent anion is free in coordination compound lattice as counter anion. Prepared product elemental analysis, theoretical value: C56.26%, H4.56%, N15.84%; Experiment value: C56.14%, H4.98%, N15.32%.
Embodiment 8
To prepare ferrocene tetrazole bipyridyl cadmium salt, its formula is [Ma(L1)b(L2)c](L3)dN (sol), in formula, M is Cd2+、L1For 2,2-bipyridyl, L2For ferrocene tetrazole univalent anion, a=1, b=2, c=2, d=0, n=0, preparation method is as follows:
In embodiment 1, MnCl used2·4H2O is with equimolar Cd (CH3COO)2·2H2O replaces, and other steps are identical with embodiment 1, and filtrate stands 5 days under the dustless condition of room temperature, obtains orange crystals ferrocene tetrazole bipyridyl cadmium salt, and calculating its productivity according to Cd is 69%.
The mono-crystalline structures of prepared ferrocene tetrazole bipyridyl cadmium salt is shown in Fig. 8, belongs to anorthic system, P-1 space group, and cell parameter a isB isC isα is 89.928 (2) °, β is 78.602 (2) °, γ is 78.222 (2) °. The separate unit of this metal complex exists independent Cd (II) ion, two neutrality 2,2-bipyridyl molecule, two ferrocene tetrazole univalent anions, wherein 2,2-bipyridyls and ferrocene tetrazole univalent anion participate in coordination with central metallic ions effect. Prepared product elemental analysis, theoretical value: C48.35%, H3.28%, N16.11%; Experiment value: C47.63%, H4.15%, N15.82%.
Embodiment 9
To prepare ferrocene tetrazole Phen cadmium salt, its formula is [Ma(L1)b(L2)c](L3)dN (sol), in formula, M is Cd2+、L1For 1,10-Phen, L2For H2O、L3For ferrocene tetrazole univalent anion, a=1, b=2, c=2, d=2, n=0, preparation method is as follows:
In embodiment 8,2,2-bipyridyls used are with equimolar 1,10-Phen is replaced, and other steps are identical with embodiment 8, and filtrate stands 1 day under the dustless condition of room temperature, obtaining orange crystals ferrocene tetrazole Phen cadmium salt, calculating its productivity according to Cd is 73%.
The mono-crystalline structures of prepared ferrocene tetrazole Phen cadmium salt is shown in Fig. 9, belongs to monoclinic system, P2 (1)/c space group, and cell parameter a isB isC isα is 90 °, β is 95.1240 (10) °, γ is 90 °. The separate unit of this metal complex exists independent Cd (II) ion, two neutrality 1,10-Phen molecule, two hydrones, wherein 1,10-Phen and hydrone and central metallic ions effect participate in coordination, and two other ferrocene tetrazole univalent anion is free in coordination compound lattice as counter anion. Prepared product elemental analysis, theoretical value: C54.43%, H3.77%, N16.56%; Experiment value: C53.64%, H4.35%, N15.97%.
Embodiment 10
To prepare ferrocene tetrazole Phen lead salt, its formula is [Ma(L1)b(L2)c](L3)dN (sol), in formula, M is Pb2+、L1For 1,10-Phen, L2For CO3 2-、L3Being free 1,10-Phen molecule, a=2, b=4, c=1, d=2, n=1 for ferrocene tetrazole univalent anion, sol, preparation method is as follows:
In example 2, MnCl used2·4H2O is with equimolar Pb (CH3COO)2·3H2O replaces, and other steps are identical with embodiment 2, and filtrate stands 30 days under the dustless condition of room temperature, obtains orange crystals ferrocene tetrazole Phen lead salt, and calculating its productivity according to Pb is 76%.
The mono-crystalline structures of prepared ferrocene tetrazole Phen lead salt is shown in Figure 10, belongs to anorthic system, P-1 space group, and cell parameter a isB isC isα is 83.106 (2) °, β is 82.671 (2) °, γ is 78.580 (2) °. The separate unit of this metal complex exists two independent Pb (II) ions, four each and every one neutrality 1,10-Phen molecule, a carbonate dianion, wherein 1,10-Phen and carbonate and central metallic ions effect participate in coordination, two other ferrocene tetrazole univalent anion and neutrality 1, a 10-Phen molecule are free in coordination compound lattice as counter anion. Prepared product elemental analysis, theoretical value: C59.34%, H3.48%, N15.01%; Experiment value: C58.74%, H4.35%, N14.63%.
In order to prove beneficial effects of the present invention, inventor is for ammonium perchlorate (AP), and the catalytic performance of ferrocene tetrazole metal complex prepared by embodiment 1-10 is tested, and specific experiment situation is as follows:
Taking ferrocene tetrazole metal complex 5mg, pulverous AP95mg, ground and mixed is uniform, adopts thermal analyzer that its catalytic performance is tested, and experimental result is shown in Figure 11.
As seen from Figure 11, the thermal decomposition of AP can be divided into three phases: the first stage is the decalescence process of AP, it is changed into cubic system by rhombic system, peak temperature is 249.0 DEG C, second stage is the low-temperature decomposition process of AP, peak temperature is 293.7 DEG C, phase III is the endothermic process following the low-temperature decomposition stage closely, it is called the pyrolytic stage, this pyrolysis process both can be endothermic process can also be exothermic process, depending primarily on the competition between distillation and thermal decomposition, peak temperature is 429.3 DEG C. When after the ferrocene tetrazole metal complex adding 5% embodiment 1～10 preparation in AP, the low-temperature decomposition stage of AP is advanced to 189.2～203.7 DEG C, the pyrolytic stage is advanced to 299.7～344 DEG C and liberated heat relatively AP significantly increases, and terminates decomposition temperature and is advanced to 312～365.8 DEG C. As can be seen here, compared with pure AP, after adding the compounds of this invention, the most strongly exothermic peak temperature of system all shifts to an earlier date, and liberated heat substantially increases, and illustrates that the thermal decomposition of AP is had good combustion catalysis by the compounds of this invention.
Claims (2)
1. a ferrocene tetrazole metal complex, it is characterised in that: the formula of this coordination compound is [Ma(L1)b(L2)c](L3)dN (sol);
In formula, M is Mn2+、L1For 2,2-bipyridyl, L2For H2O、L3During for ferrocene tetrazole univalent anion, a=1, b=1, c=4, d=2, n=0, this coordination compound belongs to monoclinic system, P2 (1)/c space group, and cell parameter a isB isC isα is 90 °, β is 102.249 (2) °, γ is 90 °;
In formula, M is Mn2+、L1For 1,10-Phen, L2For H2O、L3During for ferrocene tetrazole univalent anion, a=1, b=2, c=2, d=2, n=0, this coordination compound belongs to monoclinic system, P2 (1)/c space group, and cell parameter a isB isC isα is 90 °, β is 95.234 (2) °, γ is 90 °;
In formula, M is Co2+、L1For 1,10-Phen, L3For the H that ferrocene tetrazole univalent anion, sol are free2When O molecule, a=1, b=3, c=0, d=2, n=7, this coordination compound belongs to anorthic system, P-1 space group, and cell parameter a isB isC isα is 97.811 (2) °, β is 98.258 (2) °, γ is 109.420 (3) °;
In formula, M is Ni2+、L1For 1,10-Phen, L3For the H that ferrocene tetrazole univalent anion, sol are free2When O molecule, a=1, b=3, c=0, d=2, n=9, this coordination compound belongs to anorthic system, P-1 space group, and cell parameter a isB isC isα is 97.897 (2) °, β is 98.566 (2) °, γ is 109.431 (2) °;
In formula, M is Cu2+、L1For 2,2-bipyridyl, L2When being free ethanol molecule, a=2, b=2, c=4, d=0, n=1 for ferrocene tetrazole univalent anion, sol, this coordination compound belongs to orthorhombic system, P-1 space group, and cell parameter a isB isC isα is 90 ° of β is 90 °, γ is 90 °;
In formula, M is Cu2+、L1For 1,10-Phen, L3For the H that ferrocene tetrazole univalent anion, sol are free2When O molecule, a=1, b=3, c=0, d=2, n=8, this coordination compound belongs to anorthic system, P-1 space group, and cell parameter a isB isC isα is 98.248 (2) °, β is 97.876 (2) °, γ is 109.583 (2) °;
In formula, M is Zn2+、L1For 1,10-Phen, L3For the H that ferrocene tetrazole univalent anion, sol are free2When O molecule, a=1, b=3, c=0, d=2, n=7, this coordination compound belongs to anorthic system, P-1 space group, and cell parameter a isB isC isα is 97.942 (2) °, β is 98.722 (2) °, γ is 109.062 (3) °;
In formula, M is Cd2+、L1For 2,2-bipyridyl, L2During for ferrocene tetrazole univalent anion, a=1, b=2, c=2, d=0, n=0, this coordination compound belongs to anorthic system, P-1 space group, and cell parameter a isB isC isα is 89.928 (2) °, β is 78.602 (2) °, γ is 78.222 (2) °;
In formula, M is Cd2+、L1For 1,10-Phen, L2For H2O、L3During for ferrocene tetrazole univalent anion, a=1, b=2, c=2, d=2, n=0, this coordination compound belongs to monoclinic system, P2 (1)/c space group, and cell parameter a isB isC isα is 90 °, β is 95.1240 (10) °, γ is 90 °;
In formula, M is Pb2+、L1For 1,10-Phen, L2For CO3 2-、L3When being free 1,10-Phen molecule, a=2, b=4, c=1, d=2, n=1 for ferrocene tetrazole univalent anion, sol, this coordination compound belongs to anorthic system, P-1 space group, and cell parameter a isB isC isα is 83.106 (2) °, β is 82.671 (2) °, γ is 78.580 (2) °.
2. the preparation method of the ferrocene tetrazole metal complex of a claim 1, it is characterized in that: water-soluble metal salt is dissolved completely in distilled water, it is subsequently adding and is dissolved completely in the 1 of dehydrated alcohol, 10-Phen or 2, 2-bipyridyl solution, stir, add the ferrocene tetrazole sodium salt solution being dissolved completely in distilled water, water-soluble metal salt, 1, 10-Phen or 2, 2-bipyridyl, the mol ratio of ferrocene tetrazole sodium salt is 1:2:2, stir 20～30 minutes, filter, filtrate is stood to forming crystal under the dustless condition of room temperature, namely ferrocene tetrazole metal complex is obtained,
Above-mentioned water-soluble metal salt is Mn2+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+、Pb2+In any one villaumite or acetate.
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