CN108558957A - N- ferrocenyl methyl -3- amino-1,2,4-triazols transient metal complex containing energy and preparation method thereof - Google Patents
N- ferrocenyl methyl -3- amino-1,2,4-triazols transient metal complex containing energy and preparation method thereof Download PDFInfo
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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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
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- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D5/00—Fertilisers containing magnesium
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
- C06B29/22—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate the salt being ammonium perchlorate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
Abstract
The invention discloses a kind of 3 amino of N ferrocenyls methyl, 1,2,4 triazole transient metal complexes containing energy and preparation method thereof, and the structural formula of the complex is：M represents Cu, Zn, Mn, Ni, Co, Cd or Fe, L 1H, 1'H (5,5' bis- tetrazoliums) 1,1' diol dianions, the integer that x is 0~3 in formula.Complex preparation method of the present invention is simple, it is at low cost, yield is high, there is preferable combustion catalysis to composite solidpropellant major constituent ammonium perchlorate and hexogen, 3 amino 1 of N ferrocenyls methyl therein, 2,4 Triazole ligand nitrogen contents are high, there is the higher positive enthalpy of formation, there is concerted catalysis effect, energy-containing compound 1 with transition metal ions, 1' dihydroxy 5, the introducing of 5' bistetrazole disodium salt tetrahydrates can not only make the reduction of burningrate catalyst sensitivity, and can be that solid propellant contributes energy, and it is environmentally friendly to decompose the nitrogen released.
Description
Technical field
The invention belongs to solid propellant technical fields, and in particular to a kind of N- ferrocenyls methyl -3- amino -1,2,4-
The preparation method of triazole transient metal complex containing energy and the complex.
Background technology
With the development of modern national defense technology, guided missile (including improves to the performance for improving tactical missile in many countries
Range, mobility and flying speed) increasingly keen interest is shown, this just proposes the energy of engine and propellant
Increasingly higher demands.No matter required from the miniaturization of strategic missile, Mobile launch, hidden, inexpensive and low levels of maintenance,
Or from the signal of tactical missile and prominent anti-, environment, mobility (thrust adjusting), increase range, vulnerability requires and space flight
The requirements such as field high energy, " cleaning ", all so that solid propellant research must be comprehensive to raising propellant energy density, improvement
The direction that can and reduce cost is developed.
Ferrocene is also known as bicyclic luxuriant dialkylene iron, it is a kind of metallo-organic compound with interlayer structure.Ferrocene
And its derivative because of itself the characteristics of, such as hydrophobicity, biological oxidability, armaticity, stability, hypotoxicity, bioactivity
Deng and be widely used.Ferrocene and its derivative is as end hydroxy butadiene (HTPB) and carboxyl-terminated polybutadiene (CTPB)
The burningrate catalyst of propellant is more more effective than catalyst such as the iron oxide of inorganic, ferric ferricyanides.Certain ferrocene derivatives are not
It is only capable of improving the mechanical property and processing performance of propellant, also has the function of reducing pressure index.Reduce ferrocene class burn rate
The volatility and migration of catalyst increase its iron-holder, improve its burn rate catalytic effect, are always the important of domestic and foreign scholars
Research topic.
Efficient burningrate catalyst-biferrocene that German Wei Ba Oil Co., Ltd produces composite solidpropellant spreads out
Biological Kato pungent (Catocene, 2,2'- bis--(ethyl dicyclopentadienyl iron) propane), BBFPr (2,2'- bis--(butyl ferrocene) propane)
With BBFPe (1,1'- bis--(butyl ferrocene) pentane).French explosive wastewater company develops a kind of non-volatility and nonmigratory
Band functional group the polymer-Ba get Xin (Butacene) containing ferrocene, it is a kind of ferrocene to be connected by chemical bond
Burningrate catalyst on to hydroxyl-terminated polybutadiene prepolymer.Catocene, BBFPr, BBFPe, Butacene are four kinds and generally acknowledge
Efficient ferrocene derivatives.Bohn et al. to they adjust propellant burning rate behaviors evaluated, the results showed that they
Improving in the burn rate of propellant has significant effect.
Wang Yan in 2002 et al. has obtained a series of monosubstituted and disubstituted acyl group two by ferrocene acylation reaction
Luxuriant iron has obtained corresponding alkylferrocenes through Clemmenson reduction methods, and has had studied the electrochemistry of these alkylferrocenes
Performance and its catalytic burning-rate in composite solidpropellant.The experimental results showed that the electrochemistry of such alkylferrocenes
Property is close, is had no significant effect to catalytic burning-rate, mass fraction of the catalytic burning-rate with ferro element in compound
There is positive correlation trend.Tang Song blueness in 2004 et al. adds the derivative (RF) of hydroxyl Ferrocene, two respectively in propellant formulation
After the ester derivative (FBB) of luxuriant iron, multinuclear ferrocene derivatives (GFP) and the high burning ratemodifier of carborane class (NHC), make
Obtaining burn rate can be adjusted at 10~100mm/s (6.86~9.8MPa), and have good comprehensive performance.With tertiary butyl ferrocene
(TBF) compare, volatility size sequence is GFP<FBB<RF≤TBF, migration order are GFP<FBB<RF<TBF.
International English passes through condensation reaction, Vilsmeier formylation reactions, reduction reaction using ferrocene as raw material within 2006
Deng it is a series of to have synthesized di-ferrocene propane, carboxaldehyde radicals di-ferrocene propane, unitary methylol di-ferrocene propane (HBP) etc.
Ferrocene derivatives.Its migration and volatility as burningrate catalyst are reduced on the basis of ensureing iron-holder.
Tang's filial piety in 2008 is bright to carry out acylation reaction to ferrocene, has obtained chloroacetyl ferrocene derivative, has used differential scanning calorimeter
It has studied after being added to 5% chloroacetyl ferrocene in ammonium perchlorate so that the maximum weight loss rate peak of ammonium perchlorate (AP)
Temperature is advanced by 103.57 DEG C.
The bright progress for reviewing biferrocene nearly ten years and its derivative of Tang's filial piety in 2012.Ferrocene and its spread out
Become potential electron donor if connecting the hetero atom containing lone pair electrons on biological cyclopentadienyl ring, they can be with rubidium, caesium, postscript, platinum
Equal metallic atoms chelating forms the compound with catalytic activity.It designs, synthesize and study this kind of ferrocene complex compound and provide
Catalytic effect with concerted catalysis effect by be ferrocene derivatives research field from now on a hot spot.
Zhu schoolmates, Bian Zhanxi in 2015 et al. have synthesized the ferrocenyl β- diketonate containing phenyl and its Cu, Ni complex, add
Ferrocenyl β- diketonate or their Cu (II) or Ni (II) complex is added in AP, not only to inhibit AP high temperature to a certain extent
The distillation in thermal degradation stage, and the thermal degradation temperature of AP can be made to shift to an earlier date.Match relative to ferrocenyl β- diketonate ligand and Ni (II)
Object is closed, Cu (II) complex is better burningrate catalyst.Yuan Yao cutting edges of a knife or a sword in 2015 et al. pass through Aminoferrocene and pyrroles's -2- first
The condensation reaction of aldehyde obtains a kind of ferrocene schiff bases pyrrole ligand, and and NiCl2·6H2O coordinations synthesize ferrocene pyrroles-
Imines chelating Ni complexs have significant thermal decomposition catalytic action to solid propellant major constituent AP.2015, Wang Chunyan et al.
With ferrocene tetrazole for main ligand, 2,2- bipyridyls and 1,10- Phens are assistant ligand, and one is formd with transition metal
The ferrocene tetrazole metal complex of series.W.H.Mahmoud in 2017 et al. is by 2- ferrocenyl methyl ketones and 2- aminobenzenes
Phenol prepares a kind of novel ferrocene schiff base ligand by aldimine condensation reaction, and with transition metal ions and 1,10- is adjacent
Phenanthroline reaction generates a series of transient metal complexes.
Overcome Ferrocene and its derivative volatility and migration be still ferrocene class burningrate catalyst development core
Target centroid, exploitation migration and the comprehensive performance novel ferrocene class burn rate outstanding that volatility is low, burning regulation performance is excellent
Catalyst is still the hot spot of this research field.
Invention content
Technical problem to be solved by the present invention lies in overcome existing ferrocene class burningrate catalyst it is easy to migrate, it is volatile,
The low disadvantage of energy, providing one kind, thermal stability is good under field conditions (factors), itself has higher generation heat and the combustion heat, and urge
Change the adjustable N- ferrocenyls methyl -3- amino -1,2 of performance, 4- triazoles transient metal complex containing energy, and is the complex
A kind of easy to operate, lower-cost preparation method is provided.
Solve N- ferrocenyl methyl -3- amino-1,2,4-triazols transition containing energy gold used by above-mentioned technical problem
The structural formula of metal complex is as follows：
M represents Cu, Zn, Mn, Ni, Co, Cd or Fe, L 1H, 1'H- (5,5'- bis- tetrazoliums) -1,1'- glycol divalent in formula
Anion, the integer that x is 0~3.
The preparation method of N- ferrocenyls methyl -3- amino-1,2,4-triazols of the present invention transient metal complex containing energy
For：Divalent metal salt is dissolved in distilled water, N- ferrocenyl methyl -3- is added dropwise simultaneously thereto under the conditions of 60~70 DEG C
The ethanol solution of amino-1,2,4-triazol and 1,1'- dihydroxy -5,5'- bistetrazole disodium salt tetrahydrates it is water-soluble
Liquid drips rear constant temperature and is stirred to react 3~5 hours, filtering, and with absolute ethyl alcohol, distillation water washing, vacuum drying obtains N- bis-
Luxuriant iron-based methyl -3- amino-1,2,4-triazols transient metal complex containing energy.
Above-mentioned divalent metal salt is the perchlorate or frerrous chloride of metallic copper, zinc, manganese, nickel, cobalt, cadmium.
Above-mentioned divalent metal salt and N- ferrocenyl methyl -3- amino-1,2,4-triazols ligand, 1,1'- dihydroxy -
The molar ratio of 5,5'- bistetrazole disodium salt tetrahydrates is 1:(2~2.5):1, wherein amino -1 N- ferrocenyls methyl -3-,
The structure of 2,4- triazoles is：
Preparation method is：It is 1 in molar ratio by ferrocene carboxaldehyde and 3- amino-1,2,4-triazols:1.25 being dissolved in
Reaction, which reaches, in absolute ethyl alcohol, after reflux 8 hours balances, and solvent, gained red oil silica gel column chromatography, eluent is evaporated off
It is 1 for absolute ethyl alcohol and petroleum ether volume ratio:5 mixed liquor removes solvent and obtains ferrocene triazole schiff base ligand.By institute
It obtains ferrocene triazole schiff base ligand to be dissolved in absolute methanol, the sodium borohydride solids of 1.2 times of equivalents is added under ice salt bath, rise
To room temperature reaction 2 hours, after reaction, a small amount of water is added and removes remaining sodium borohydride, is concentrated under reduced pressure, with dichloromethane and
Water extracts, and detaches organic layer, is concentrated under reduced pressure into sediment volume, and n-hexane is added and precipitates product, filters, and vacuum drying obtains
To N- ferrocenyl methyl -3- amino -1,2,4- Triazole ligands, yield 73.3%.
N- ferrocenyls methyl -3- amino-1,2,4-triazols of the present invention transient metal complex containing energy is with N- ferrocene
Ylmethyl -3- amino -1,2,4- triazoles are neutral ligand, and 1,1'- dihydroxy -5,5'- bistetrazole disodium salt tetrahydrate is
Anion ligand has the following advantages：
1, complex of the present invention be transient metal complex, not volatile under field conditions (factors), thermal stability is good, have compared with
High generation heat and the combustion heat, migration and volatility are extremely low, advantageously account for ferrocene class combustionregulator in propellant
Existing easy to migrate and volatile problem.
2, N- ferrocenyls methyl -3- amino-1,2,4-triazol ligands used in complex of the present invention are than traditional
Schiff base ligand chemical property is stablized, and storage can be stablized；Four water of anion ligand 1,1'- dihydroxy -5,5'- bistetrazoles disodium salt
Closing object, not only nitrogen content is high, can make the reduction of burningrate catalyst sensitivity, and can be that solid propellant contributes energy.
3, complex of the present invention can regulate and control the catalytic performance of composite solidpropellant major constituent ammonium perchlorate and hexogen,
Susceptibility of the burn rate by pressure and temperature effect for reducing propellant, adjusts propellant at the combustion stability for improving propellant
Burn rate, to realize different thrust schemes that propellant design is wanted.
4, complex preparation method of the present invention is simple, and cost is relatively low, and yield is higher, overcomes existing ferrocene class burn rate and urges
The shortcomings of agent synthesis technology is cumbersome, of high cost, synthesis cycle is long.
Description of the drawings
Fig. 1 is the differential scanning calorimetric analysis that 5% Examples 1 to 7 complex is added in ammonium perchlorate.
Fig. 2 is the differential scanning calorimetric analysis that 5% Examples 1 to 7 complex is added in hexogen.
Fig. 3 is the thermal gravimetric analysis curve of Examples 1 to 4 complex.
Fig. 4 is the thermal gravimetric analysis curve of 5~7 complex of embodiment.
Specific implementation mode
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
By 0.09g (0.25mmol) Cu (ClO4)2·6H2O is dissolved in the 100mL round-bottomed flasks for filling 10mL distilled water,
When temperature rises to 60 DEG C, it is added dropwise simultaneously is dissolved in 20mL dissolved with 0.14g (0.5mmol) N- ferrocenyls methyl-thereto
The ethanol solution and 10mL of 3- amino-1,2,4-triazols are dissolved with 0.05g (0.25mmol) 1,1'- dihydroxy -5,5'-
The aqueous solution of bistetrazole disodium salt tetrahydrate drips rear constant temperature and is stirred to react 2 hours, has precipitation to generate, and nothing is used in combination in filtering
Water-ethanol, distillation water washing filter cake, normal-temperature vacuum drying obtain the following N- ferrocenyl methyl -3- amino -1,2 of structural formula,
4- triazoles Cu complexs containing energy：
Its yield is 59.9%, and structural characterization data are：IR(KBr,cm-1):3391(s,br),3107(m),2362(w),
1626(s),1590(s),1439(vs),1253(vs),1182(s),1102(m),1005(m),836(w),748(s),491
(m)cm-1, elemental analysis (being calculated value in bracket):C%38.47 (38.66), H%4.39 (4.59), N%24.75
(24.87).
Embodiment 2
In the present embodiment, with equimolar Zn (ClO4)2·6H2Cu (ClO in O alternative embodiments 14)2·6H2O, when reaction
Between extend to 3 hours, other steps are same as Example 1, obtain following amino -1 N- ferrocenyl methyl -3- of structural formula,
2,4- triazoles Zn complexs containing energy：
Its yield is 32.21%, and structural characterization data are：IR(KBr,cm-1):3391(vs,br),1617(s),1563
(m),1439(vs),1253(vs),1182(s),1013(m),836(w),748(s),491(m)cm–1, elemental analysis is (in bracket
For calculated value):C%39.80 (39.37), H%4.78 (4.44), N%25.75 (25.33)
Embodiment 3
In the present embodiment, with equimolar Mn (ClO4)2·6H2Cu (ClO in O alternative embodiments 14)2·6H2O, when reaction
Between extend to 5 hours, other steps are same as Example 1, obtain following amino -1 N- ferrocenyl methyl -3- of structural formula,
2,4- triazoles Mn complexs containing energy：
Its yield is 50.86%, and structural characterization data are：IR(KBr,cm-1):3374(vs,br),1617(s),1546
(m),1439(vs),1253(vs),1182(s),1013(m),836(w),748(m),491(m)cm–1, elemental analysis is (in bracket
For calculated value):C%41.80 (41.55), H%4.57 (4.21), N%26.46 (26.73)
Embodiment 4
In the present embodiment, with equimolar Ni (ClO4)2·6H2Cu (ClO in O alternative embodiments 14)2·6H2O, when reaction
Between extend to 5 hours, other steps are same as Example 1, obtain following amino -1 N- ferrocenyl methyl -3- of structural formula,
2,4- triazoles Ni complexs containing energy：
Its yield is 73.92%, and structural characterization data are：IR(KBr,cm-1):3383(s,br),2362(m),1617
(vs),1546(m),1439(s),1253(s),1182(m),1102(m),1013(m),819(m),739(m),491(s)cm–1,
Elemental analysis (being calculated value in bracket):C%39.80 (39.67), H%4.82 (4.48), N%25.73 (25.52)
Embodiment 5
In the present embodiment, with equimolar Co (ClO4)2·6H2Cu (ClO in O alternative embodiments 14)2·6H2O, when reaction
Between extend to 5 hours, other steps are same as Example 1, obtain following amino -1 N- ferrocenyl methyl -3- of structural formula,
2,4- triazoles Co complexs containing energy：
Its yield is 36.5%, and structural characterization data are：IR(KBr,cm-1):3400(vs,br),1617(s),1563
(s),1439(vs),1253(vs),1182(s),1102(m),1013(m),739(s),482(m)cm–1, elemental analysis (bracket
Interior is calculated value):C%39.80 (39.66), H%4.63 (4.48), N%25.70 (25.51)
Embodiment 6
In the present embodiment, with equimolar Cd (ClO4)2·6H2Cu (ClO in O alternative embodiments 14)2·6H2O, when reaction
Between extend to 5 hours, other steps are same as Example 1, obtain following amino -1 N- ferrocenyl methyl -3- of structural formula,
2,4- triazoles Cd complexs containing energy：
Its yield is 62.5%, and structural characterization data are：IR(KBr,cm-1):3391(vs,br),1617(s),1581
(s),1439(vs),1253(vs),1005(m),748(s),482(m)cm–1, elemental analysis (being calculated value in bracket):
C%38.20 (38.12), H%4.80 (4.08), N%24.68 (24.54)
Embodiment 7
In the present embodiment, with equimolar FeCl2·4H2Cu (ClO in O alternative embodiments 14)2·6H2O, reaction time prolong
For length to 5 hours, other steps were same as Example 1, obtain the following N- ferrocenyl methyl -3- amino -1,2 of structural formula, 4-
Triazole Fe complexs containing energy：
Its yield is 24.35%, and structural characterization data are：IR(KBr,cm-1):3347(vs,br),1652(s),1617
(s),1439(vs),1253(vs),1182(s),1013(m),748(s),561(m)cm–1, elemental analysis (is theory in bracket
Calculated value):C%39.53 (39.80), H%4.80 (4.49), N%25.45 (25.60)
In order to prove beneficial effects of the present invention, inventor is by taking ammonium perchlorate (AP), hexogen (RDX) as an example, to implementing
The catalytic performance of complex prepared by example 1~7 is tested, and specific experiment situation is as follows：
1, catalytic performance test
(1) each 5mg of complex, the powdered AP 95mg that respectively prepared by Example 1~7, ground and mixed are uniform；It takes
The pungent 5mg of Kato, powdered AP 95mg, ground and mixed are uniform；Its catalytic performance is surveyed using differential scanning calorimeter
Examination, the result is shown in Figure 1.As seen from Figure 1, the thermal decomposition of AP can be divided into three phases：The decalescence process that first process is AP,
Peak temperature is 249.0 DEG C, and the peak temperature of second stage is 284.4 DEG C, is the low-temperature decomposition process of AP, the peak of phase III
It is 415.3 DEG C to be worth temperature, referred to as the pyrolytic stage, downward heat absorption is shown as from the low temperature pyrogenation stage to the pyrolytic stage
Peak, this is because stage AP is decomposed thermally to form gas (HCl, NH3) heat that is absorbed is more than itself to decompose and discharged
Heat is not obvious so the thermal decomposition process of AP itself releases heat.After adding 5% Examples 1 to 7 complex in AP,
Pyrolytic stage final temperature is advanced to 312.7~356.8 DEG C, and the heat released is up to 964.71~1453.56J/g.
It can be seen that compared with pure AP, the pyrolytic stage presentation concentration exothermic phenomenon of system after complex of the present invention, heat release are added
Peak temperature shifts to an earlier date, and the heat released obviously increases；The complex that wherein prepared by embodiment 1 and embodiment 3 urges the burning of AP
Change effect is more pungent than Kato significantly.Illustrate that complex of the present invention has good combustion catalysis to the thermal decomposition of AP.
(2) each 5mg of complex, powdered hexogen (RDX) 95mg that respectively prepared by Example 1~7, ground and mixed
Uniformly；The pungent 5mg of card taking support, powdered RDX 95mg, ground and mixed are uniform；Using differential scanning calorimeter to its catalytic performance
It is tested, as a result sees Fig. 2.From Figure 2 it can be seen that RDX has the apparent decomposition caused heat release peak, the heat of releasing to be at 229.2 DEG C
827.9J/g；After adding 5% Examples 1 to 7 complex in RDX, in addition to 2 complex of embodiment, other complexs make RDX
Thermal discharge increase, wherein 4 complex of embodiment keeps RDX thermal discharges maximum, is 1230.14J/g.The experimental results showed that this hair
Bright complex has certain catalytic action to the thermal decomposition of RDX.
2, heat stability testing
Complex 3mg, the pungent 3mg of Kato that respectively prepared by Example 1~7, using thermogravimetric analyzer to its thermal stability
It is tested, as a result sees Fig. 3 and Fig. 4.
By Fig. 3 and 4 as it can be seen that the weightless temperature of complex prepared by the embodiment of the present invention 1~7 has at 200 DEG C or more
Good thermal stability.
Claims (3)
1. a kind of N- ferrocenyls methyl -3- amino -1,2,4- triazoles transient metal complex containing energy, it is characterised in that this is matched
The structure for closing object is as follows：
M represents Cu, Zn, Mn, Ni, Co, Cd or Fe in formula, L 1H, 1'H- (5,5'- bis- tetrazoliums) -1,1'- glycol divalent the moon from
Son, the integer that x is 0~3.
2. a kind of N- ferrocenyls methyl -3- amino-1,2,4-triazols described in claim 1 transient metal complex containing energy
Preparation method, it is characterised in that：Divalent metal salt is dissolved in distilled water, is dripped simultaneously thereto under the conditions of 60~70 DEG C
Add the ethanol solution and 1,1'- dihydroxy -5,5'- bistetrazoles two of N- ferrocenyl methyl -3- amino-1,2,4-triazols
The aqueous solution of sodium salt tetrahydrate drips rear constant temperature and is stirred to react 3~5 hours, filtering, with absolute ethyl alcohol, distills water washing,
Vacuum drying obtains N- ferrocenyl methyl -3- amino -1,2,4- triazoles transient metal complex containing energy；
Above-mentioned divalent metal salt is the perchlorate or frerrous chloride of any one in copper, zinc, manganese, nickel, cobalt, cadmium.
3. N- ferrocenyls methyl -3- amino-1,2,4-triazols according to claim 2 transient metal complex containing energy
Preparation method, it is characterised in that：The divalent metal salt and N- ferrocenyl methyl -3- amino-1,2,4-triazols, 1,
The molar ratio of 1'- dihydroxy -5,5'- bistetrazole disodium salt tetrahydrates is 1:(2~2.5):1.
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