DE202010018123U1 - Explosive metal complexes, their preparation and use, as well as detonators - Google Patents

Abstract

Explosive metal complex according to one of the formulas: [M (NH3) b (N3) c] (5,5'-azotetrazolate); [M (NH 3) b (L3) c] (5-nitrotetrazolate) 2; [M (NH 3) b (L3) c] (5-Nitroaminotetrazolat) 2; [M (NH 3) b (L3) c] (5-nitrotetrazolate); [M (NH 3) b (L3) c] (5-Nitroaminotetrazolat); [M (NH3) b (NO2) c] (5,5'-azotetrazolate); [M (NH3) b (NO2) c] (5-nitrotetrazolate) 2; [M (NH3) b (NO2) c] (5-Nitroaminotetrazolat) 2; [M (NH3) b (NO2) c] (5-nitrotetrazolate); and [M (NH3) b (NO2) c] (5-nitroaminotetrazolate), where M is a metal selected from the transition metals of groups 3-12 of the IUPAC periodic table; b + c = h are h is the number of possible ligands of the metal; c> 0; and b and c are chosen such that the total net charge of the complex is 0.

Description

FIELD OF THE INVENTION

The present invention relates to explosive metal complexes with nitrogen-containing, high-energy anions of the tetrazole type and igniters containing these complexes as well as the use as initial explosive. Furthermore, the present invention relates to lead-free ignition mixtures.

BACKGROUND OF THE INVENTION

Primary explosives can be exploded by relatively weak mechanical shock, friction, or sparks, and are typically used to make explosives, propellants, fuel assemblies, and primers. The primary explosives used today are, in particular, heavy metal salts, in particular lead salts, such as, for example, lead azide and lead idiocyanate (leadrinitroresorcinate), but also silver salts, such as silver azide or organic compounds, such as diazodinitrophenol. In commercial detonators, tetrazene is often added to blends of initiating explosives to increase the reliability of the detonators.

However, the use of lead-containing explosives in the above-mentioned explosives, propellants, fuel charges or ignition charges results in the formation of toxic gaseous exhaust products which are undesirable for reasons of health and environmental protection. There is therefore a great need for the development of environmentally friendly, lead-free alternatives.

A known alternative is the use of organic compounds derived from tetrazole. These include the anions azotetrazolate (C ₂ N ₁₀ ^2- , = AZT), nitrotetrazolate (CN ₄ NO ₂ -, = NT) and nitroaminotetrazolate (CN ₄ NHNO ₂ -, = NAT) ( B. Halford: "Pyrotechnics for the Planet," Chemical & Engineering News 2008, 86, Issue 26, pp. 14-18 ). These anions are usually combined with nitrogen-containing cations such as hydrazinium, guanidinium or aminoguanidinium ( TM Klapötke et al .: "[N₂H₅] + ₂ [N₄C-NN-CN₄] ²-A New High-Nitrogen High-Energetic Material", Inorg. Chem. 2001, 40, 3570-3575 ; DE 40 34 645 A1 "Stable, nitrogen-rich compound guanidinium-5,5'-azo-tetrazolate"). Although individual transition metal derivatives of these anions, especially in the case of the AZT dianion, have long been known ( J. Thiele: "On Azo and Hydrazo Compounds of Tetrazole," Liebigs Ann. Chem. 1898, 303, 57-75 ), these are useless for practical use, since they are unpredictably explosive.

Occasionally, transition-metal complexes have been described in which the nitrotetrazolate anion as ligand is part of a complex cation. In these compounds, the nitrotetrazolate ligand is directly coordinated to the transition metal, for example trivalent cobalt ( A. Yu. Zhilin et al .: "Synthesis of a high-energy-capacity compound, tetraammine-cis-bis (nitro-2H-tetrazolato-N 2) cobalt (III) perchlorate", Russ. J. Appl. Chem. 2001, 74, 99-102 ; AV Smirnov et al .: "Synthesis of Cobalt (III) Ammine Complexes as Explosive for Safe Priming Charges", Russ. J. Appl. Chem. 2004, 77, 794-796 ). The use of anionic iron (II) complexes with coordinated 5-nitrotetrazolato ligands has also been proposed ( MHV Huynh et al .: "Green primary explosive: 5-nitrotetrazolato-N 2 -ferrate hierarchies", Proc. Natl. Acad. Sci. 2006, 103, 10322-10327 ).

So far, none of these substances has been able to assert itself on the market, since on the one hand the production costs are too high and, on the other hand, the sensitivity is unsatisfactory compared to the substances currently used.

Defined explosive compounds that comprise complex transition-metal cations in combination with the nitrogen-rich energetic anions have so far been known only for copper and silver ( TM Klapötke et al .: "Safe 5-nitrotetrazolate anion transfer reagents", Dalton Trans. 2009, 1835 ). However, the described complex copper and silver nitrotetrazolates are generally too stable to be used as primary explosives.

There is therefore still a great need for a larger class of explosive transition metal complexes with nitrogen-containing, high-energy anions, which can be used as lead-free primary explosives and overcome the disadvantages of known compounds.

One of the most important uses of explosives is its use in ignition mixtures. In the past, a large number of different ignition compounds have been prepared for use in explosive articles.

These compositions have been constantly evolving over the years.

First, igniters were filled with mercury-fulminate-based mixtures; these were unsuitable, however, as the gun barrels corroded. In the 1940's, mercury fulminate compositions were largely replaced by the pencilyphenate and tetrazene based compositions still in use today.

The principal explosive constituent of primer blends commonly used today is lead styphnate, usually in combination with a second primary explosive, such as tetracene, which is required to give the composition sufficient sensitivity to the impact (firing pulse). Because these ignition mixtures typically contain toxic elements such as lead, antimony and barium, they create a potential health hazard, especially within closed shooting ranges, where they accumulate in the atmosphere and on surfaces. For this reason, there is a need for non-toxic primer blends that can replace the lead styphnate-based primer blends that are still produced and sold.

For example, known nontoxic priming kits contain diazodinitrophenol (DDNP) together with a sensitizing explosive such as tetrazene (see also US Pat EP 0 440 873 A2 (Blount Inc.), US 4,674,409 A (Olin Corporation)). In these compositions, however, the completeness of the ignition, especially in the case of rim-firing ammunition, is insufficient. Furthermore, the requirement of a second primary explosive such as tetracene, which acts as a sensitizer in the primer, adds additional mixing and manufacturing requirements.

Other alternatives are off US 4,608,102 A which describes a diazodinitrophenol-based composition using manganese dioxide as the main oxidizing agent, US 4,363,679 A , which discloses the use of zinc peroxide as the oxidizing agent, and the French patent FR 2,628,735 B1 which discloses the use of copper oxide with the diazodinitrophenol-based mixture. Such compositions are satisfactory in toxicity, but in part they have a low flame temperature, which in turn involves disadvantages in use. US 5,516,377 A describes a composition of at least one salt of the 5-nitroaminotetrazole and at least one oxidizing agent.

SUMMARY OF THE INVENTION

The inventors of the present invention have now surprisingly found that complexes of complexed transition metals as cations and nitrogen-containing, high-energy tetrazole-type anions overcome the known disadvantages and represent an alternative to the known primary explosives. The novel complex compounds are accessible by simple metathesis reactions easily and in larger quantities.

In a first aspect, therefore, the present invention relates to a transition metal complex according to claim 1 and to ignition agents containing it according to claims 2-5.

The present invention also relates to the use of one or more of the listed explosive metal complexes according to claim 6.

Furthermore, the invention also relates to the use of an ignition means as an explosive, propellant, fuel or igniter set according to claim 7.

DESCRIPTION OF THE FIGURES

1 Figure 4 shows the structural formulas of various tetrazole-type anions which may be included in the complexes described herein. NT: 5-nitrotetrazolate; NAT: 5-nitroaminotetrazolate; AZT: 5,5'-azotetrazolate; DAAT: 5-diazoamidotetrazolate.

2 shows a micrograph of rod-shaped single crystals of [Co (NH ₃ ) ₅ N ₃ ] (AZT).

3 shows the molecular structure of [Co (NH ₃ ) ₅ N ₃ ] (AZT).

DETAILED DESCRIPTION OF THE INVENTION DEFINITIONS

Unless otherwise stated, the terms used in the claims and the description have the meanings given below.

"Alkyl" refers to a saturated aliphatic hydrocarbon including straight and branched chain groups. Preferably, the alkyl group has 1 to 10 carbon atoms (when a numerical range of, for example, "1-10" is given herein, it is meant that this group, in this case the alkyl group, 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc. to including 10 carbon atoms inclusive). In particular, the alkyl may be a middle alkyl having 1 to 6 carbon atoms or a lower alkyl having 1 to 4 carbon atoms, e.g. For example, methyl, ethyl, n-propyl, isopropyl, butyl, iso-butyl, tert-butyl, etc., act. The alkyl group may be substituted or unsubstituted. When substituted, the substituent is one or more groups, for example, one or two groups independently selected from C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₄ aryl, a 5-10 membered heteroaryl ring in the 1 to 4 ring atoms independently Nitrogen, oxygen or sulfur, a 5-10 membered heteroalicyclic ring in which 1 to 3 ring atoms are independently nitrogen, oxygen or sulfur, hydroxy, C ₁ -C ₁₀ alkoxy, C ₃ -C ₈ cycloalkoxy, aryloxy, mercapto, alkylthio, Arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amide, N-amide, C-carboxy, O-carboxy, nitro, silyl, sulfinyl, sulfonyl, Amino and -NR ⁷ R ⁸ wherein R ⁷ and R ^{8 are} independently hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₄ aryl, carbonyl, acetyl, sulfonyl or amino, or R ⁷ and R ⁸ together with the nitrogen atom to which they are attached form a five- or six-membered heteroalicyclic ring. In a particular embodiment, the substituent (s) are / are selected from chlorine, fluorine, bromine, iodine, hydroxy, methoxy, carboxy, amino or -NR ⁷ R ⁸ .

A "cycloalkyl" group refers to monocyclic or polycyclic (multiple rings having common carbon atoms) groups of 3-8 carbon atoms in which the ring does not have a complete conjugated pi-electron system, e.g. Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, etc. Examples of cycloalkyl groups are cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, adamantane, cyclohexadiene, cycloheptane and cycloheptatriene. A cycloalkyl group may be substituted or unsubstituted. When substituted, the substituent group is one or more, for example one or two, independently selected from C ₁ -C ₁₀ alkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₄ aryl, a 5-10 membered heteroaryl ring wherein 1 to 4 ring atoms are independently nitrogen, oxygen or sulfur, a 5-10 membered heteroalicyclic ring in which 1 to 3 ring atoms are independently nitrogen, oxygen or sulfur, hydroxy, C ₁ -C ₁₀ alkoxy, C ₃ -C ₈ cycloalkoxy , Aryloxy, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amide, N-amide, C-carboxy, O-carboxy, nitro , Silyl, sulfinyl, sulfonyl, amino and -NR ⁷ R ⁸ wherein R ⁷ and R ^{8 are} as defined above. In a particular embodiment, the substituent (s) are / are selected from chlorine, fluorine, bromine, iodine, hydroxy, methoxy, carboxy, amino or -NR ⁷ R ⁸ .

"Alkenyl" refers to an alkyl group as defined herein which may be substituted or unsubstituted and which consists of at least two carbon atoms and at least one carbon-carbon double bond, e.g. Ethenyl, propenyl, butenyl or pentenyl and their structural isomers such as 1- or 2-propenyl, 1-, 2- or 3-butenyl, etc.

"Alkynyl" refers to an alkyl group as defined herein which may be substituted or unsubstituted and which consists of at least two carbon atoms and at least one carbon-carbon triple bond, e.g. Ethynyl (acetylene), propynyl, butynyl or petinyl and their structural isomers as described above.

"Aryl" refers to monocyclic or polycyclic (ie, rings that share adjacent carbon atoms) groups of 6 to 14 carbon ring atoms that possess a complete conjugated pi-electron system. Examples of aryl groups are phenyl, naphthalenyl and anthracenyl. The aryl group may be substituted or unsubstituted. When substituted, the substituent group is one or more, for example one or two, independently selected from C ₁ -C ₁₀ alkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₄ aryl, a 5-10 membered heteroaryl ring wherein 1 to 4 ring atoms are independently nitrogen, oxygen or sulfur, a 5-10 membered heteroalicyclic ring in which 1 to 3 ring atoms are independently nitrogen, oxygen or sulfur, hydroxy, C ₁ -C ₁₀ alkoxy, C ₃ -C ₈ cycloalkoxy , Aryloxy, mercapto, alkylthio, arylthio, cyano, halogen, trihalomethyl, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amide, N-amide, C-carboxy, O-carboxy , Nitro, silyl, sulfinyl, sulfonyl, amino and -NR ⁷ R ⁸ wherein R ⁷ and R ^{8 are} as defined above. In a particular embodiment the substituent (s) is / are selected from chlorine, fluorine, bromine, iodine, hydroxy, methoxy, carboxy, amino or -NR ⁷ R ⁸ .

A "heteroaryl" group refers to an aromatic, monocyclic group or a group of fused (ie, rings sharing an adjacent ring atom pair), aromatic rings of 5 to 10 ring atoms, where one, two, three or four ring atoms are nitrogen, Oxygen or sulfur and the rest is carbon. Examples of heteroaryl groups are pyridyl, pyrrolyl, furyl, thienyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,3-oxadiazolyl, 1, 2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,3,4-triazinyl, 1,2,3-triazinyl, benzofuryl, isobenzofuryl, benzothienyl, benzotriazolyl, isobenzothienyl, indolyl, Isoindolyl, 3H-indolyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, quinolizinyl, quinazolinyl, pthalazinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, quinolyl, isoquinolyl, tetrazolyl, 5,6,7,8-tetrahydroquinolyl, 5,6,7,8-tetrahydroisoquinolyl, Purinyl, pteridinyl, pyridinyl, pyrimidinyl, carbazolyl, xanthenyl or benzoquinolyl. The heteroaryl group may be substituted or unsubstituted. When substituted, the substituent group is one or more, for example one or two, independently selected from C ₁ -C ₁₀ alkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₄ aryl, a 5-10 membered heteroaryl ring wherein 1 to 4 ring atoms are independently nitrogen, oxygen or sulfur, a 5-10 membered heteroalicyclic ring in which 1 to 3 ring atoms are independently nitrogen, oxygen or sulfur, hydroxy, C ₁ -C ₁₀ alkoxy, C ₃ -C ₈ cycloalkoxy , Aryloxy, mercapto, alkylthio, arylthio, cyano, halogen, trihalomethyl, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amide, N-amide, C-carboxy, O-carboxy , Nitro, silyl, sulfinyl, sulfonyl, amino and -NR ⁷ R ⁸ , wherein R ⁷ and R ^{8 are} as defined above. In a particular embodiment, the substituent (s) are / are selected from chlorine, fluorine, bromine, iodine, hydroxy, methoxy, carboxy, amino or -NR ⁷ R ⁸ .

A "heteroalicyclic" group refers to a monocyclic or fused ring of 5 to 10 ring atoms containing one, two or three heteroatoms selected from nitrogen, oxygen and -S (O) _n wherein n is 0-2 and the rest of the ring atoms is carbon. The ring may also have one or more double bonds. However, the ring does not have a complete conjugated pi-electron system. Examples of heteroalicyclic groups include pyrrolidine, piperidine, piperazine, morpholine, imidazolidine, tetrahydropyridazine, tetrahydrofuran, thiomorpholine, tetrahydropyridine, and the like. The heteroalicyclic ring may be substituted or unsubstituted. When substituted, the substituent group is one or more, for example one or two, independently selected from C ₁ -C ₁₀ alkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₄ aryl, a 5-10 membered heteroaryl ring wherein 1 to 4 ring atoms are independently nitrogen, oxygen or sulfur, a 5-10 membered heteroalicyclic ring in which 1 to 3 ring atoms are independently nitrogen, oxygen or sulfur, hydroxy, C ₁ -C ₁₀ alkoxy, C ₃ -C ₈ cycloalkoxy , Aryloxy, mercapto, alkylthio, arylthio, cyano, halogen, trihalomethyl, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amide, N-amide, C-carboxy, O-carboxy , Nitro, silyl, sulfinyl, sulfonyl, amino and -NR ⁷ R ⁸ , wherein R ⁷ and R ^{8 are} as defined above. In a particular embodiment, the substituent (s) are / are selected from chlorine, fluorine, bromine, iodine, hydroxy, methoxy, carboxy, amino or -NR ⁷ R ⁸ .

A "hydroxy" group refers to an -OH group.

An "alkoxy" group refers to an -O-unsubstituted and -O-substituted alkyl group, wherein alkyl is as defined herein. Examples include methoxy, ethoxy, propoxy, butoxy, etc.

A "cycloalkoxy" group refers to an -O-cycloalkyl group wherein cycloalkyl is as defined herein and may be substituted or unsubstituted. An example is cyclopropyloxy.

An "aryloxy" group refers to an -O-aryl or -O-heteroaryl group, wherein aryl and heteroaryl are as defined herein and may each be substituted or unsubstituted. Examples include phenoxy, naphthyloxy, pyridyloxy, furanyloxy, etc. A "mercapto" group refers to a -SH group.

An "alkylthio" group refers to both an -S-alkyl and an -S-cycloalkyl group, wherein alkyl and cycloalkyl are as defined herein and may each be substituted or unsubstituted. Examples include methylthio, ethylthio, etc.

An "arylthio" group refers to both an -S-aryl and an -S-heteroaryl group, wherein Arly and heteroaryl are as defined herein and may each be substituted or unsubstituted. Examples include phenylthio, naphthylthio, pyridylthio, furanylthio, etc.

A "sulfinyl" group refers to an -S (O) -R "group wherein R" is selected from hydrogen, hydroxy, alkyl, cycloalkyl, aryl, heteroaryl (attached via a ring carbon atom) and a heteroalicyclic ring (attached via a ring carbon atom) as defined herein.

A "sulfonyl" group refers to a -S (O) ₂ -R "group wherein R" is hydrogen, hydroxy, alkyl, cycloalkyl, aryl, heteroaryl (attached via a ring carbon atom) and a heteroalicyclic ring (attached via a ring carbon atom) as defined herein.

A "trihalomethyl" group refers to a -CX ₃ group wherein X is a halogen as defined herein, for example, trifluoromethyl, trichloromethyl, tribromomethyl, dichlorofluoromethyl, etc.

"Carbonyl" refers to a -C (= O) -R "group wherein R" is selected from hydrogen, alkyl, cycloalkyl, aryl, heteroaryl (attached via a ring carbon atom) and a heteroalicyclic ring (attached via a ring carbon atom), as defined herein. Exemplary groups are acetyl, propionyl, benzoyl, formyl, cyclopropylcarbonyl, pyridinylcarbonyl, pyrrolidin-1-ylcarbonyl, etc.

A "thiocarbonyl" group refers to a -C (= S) -R "group, where R" is as defined above.

The terms "C-carboxy" and "carboxy" used interchangeably herein refer to a -C (= O) O-R "group wherein R" is as defined above, e.g. For example, -COOH, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, etc.

An "O-carboxy" group refers to an -OC (= O) R "group, where R" is as defined above, e.g. Methylcarbonyloxy, phenylcarbonyloxy, benzylcarbonyloxy, etc.

An "acetyl" group refers to a -C (= O) CH ₃ group.

A "carboxylic acid" group refers to a C-carboxy group in which R "is hydrogen.

A "halo" or "halo" group refers to fluorine, chlorine, bromine or iodine.

A "cyano" group refers to a -CN group.

A "nitro" group refers to a -NO ₂ group.

An "O-carbamyl" group refers to an -OC (= O) NR ⁷ R ⁸ group, wherein R ⁷ and R ^{8 are} as defined above.

An "N-carbamyl" group refers to an R ⁸ OC (= O) NR ⁷ group wherein R ⁷ and R ^{8 are} as defined above.

An "O-thiocarbamyl" group refers to an -OC (= S) NR ⁷ R ⁸ group, wherein R ⁷ and R ^{8 are} as defined above.

An "N-thiocarbamyl" group refers to an R ⁸ OC (= S) NR ⁷ group, wherein R ⁷ and R ^{8 are} as defined above.

An "amino" group refers to an -NR ⁷ R ⁸ group, wherein R ⁷ and R ^{8 are} independently hydrogen or unsubstituted lower alkyl, such as e.g. B. -NH ₂ , dimethylamino, diethylamino, ethylamino, methylamino, etc.

A "C-amide" group refers to a -C (= O) NR ⁷ R ⁸ group, wherein R ⁷ and R ^{8 are} as defined above. For example, R ^{7 is} hydrogen or unsubstituted C ₁ -C ₄ alkyl and R ⁸ is hydrogen, C ₁ -C ₄ alkyl optionally substituted with a heteroalicyclic ring, hydroxy or amino. C (= O) NR ⁷ R ⁸ may be, for example, aminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, diethylaminoethylaminocarbonyl, ethylaminoethylaminocarbonyl, etc.

An "N-amide" group refers to an R ⁸ C (= O) NR ⁷ group, wherein R ⁷ and R ^{8 are} as defined above, e.g. Acetylamino, etc.

In the context of the present invention, the term "neutral ligand" refers to an uncharged molecule that can form a Werner-type octahedral complex with a cobalt (III) ion. Exemplary ligands capable of this include, but are not limited to, amino group-containing organic compounds such as ethylenediamine, NH _3, and H ₂ O.

"Organo-substituted" as used herein refers to the substitution of a molecule with an organic substituent.

"Transition metal" as used herein refers to a metal of Groups 3-12 of the IUPAC Periodic Table. Transition metals include, but are not limited to: scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), Copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), Silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg).

"Number of charges" refers to the number of charges a particular ion carries. For example, a metallic cation such as Co ³⁺ has the charge number 3.

EMBODIMENTS

wobei
M ein Metall ist, das ausgewählt wird aus den Übergangsmetallen der Gruppen 3–12 des IUPAC Periodensystems,
L ein Neutralligand ist;
X ein Anion ist;
R¹ -NR²R³ oder -N=N-R⁴ ist,
R² und R³ unabhängig voneinander ausgewählt werden aus der Gruppe bestehend aus H, O, NO₂, substituiertem oder unsubstituiertem Alkyl, substituiertem oder unsubstituiertem Alkenyl und substituiertem oder unsubstituiertem Alkinyl;
R⁴ ausgewählt wird aus der Gruppe bestehend aus H, substituiertem oder unsubstituiertem Alkyl, substituiertem oder unsubstituiertem Alkenyl, substituiertem oder unsubstituiertem Alkinyl, substituiertem oder unsubstituiertem Aryl, substituiertem oder unsubstituiertem Heteroaryl und -NR⁵;
R⁵ ausgewählt wird aus der Gruppe bestehend aus H, Amino, substituiertem oder unsubstituiertem Alkyl, substituiertem oder unsubstituiertem Alkenyl, substituiertem oder unsubstituiertem Alkinyl, substituiertem oder unsubstituiertem Aryl und substituiertem oder unsubstituiertem Heteroaryl;
m eine ganze Zahl von 0 bis 6 ist;
n eine ganze Zahl von 0 bis 5 ist, wobei n ≤ (h – m) ist und wobei n und m nicht beide 0 sind; h die Anzahl der möglichen Liganden des Metalls ist;
p(a – n) ist, wobei a die Ladungszahl von M ist und p mindestens 1 ist; und
q und r jeweils eine ganze Zahl von 1 bis 3 sind.Described herein are explosive metal complexes of formula I:

in which
M is a metal selected from transition metals of Groups 3-12 of the IUPAC Periodic Table,
L is a neutral ligand;
X is an anion;
R ^{1 is} -NR ² R ³ or -N = NR ⁴ ,
R ² and R ^{3 are} independently selected from the group consisting of H, O, NO ₂ , substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl and substituted or unsubstituted alkynyl;
R ^{4 is} selected from the group consisting of H, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and -NR ⁵ ;
R ^{5 is} selected from the group consisting of H, amino, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl;
m is an integer from 0 to 6;
n is an integer from 0 to 5, where n ≤ (h-m) and where n and m are not both 0; h is the number of possible ligands of the metal;
p is (a - n), where a is the charge number of M and p is at least 1; and
q and r are each an integer from 1 to 3.

These complexes are explosive and therefore suitable as primary explosives.

In various embodiments of the explosive metal complexes, the transition metal M is selected from the group consisting of: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh In other embodiments, M is selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn , Mo, Pd, W, Re, Os and Ir. In still other embodiments, M is selected from Ti, V, Cr, Mn, Fe, Co, Ni, and Zn. In one embodiment, M is Co. In various embodiments of the metal complexes of the invention, M is not Cu or Ag.

In various embodiments of the explosive metal complexes, each neutral ligand L is independently selected from the group consisting of O (R ⁶ ) ₂ and N (R ⁶ ) ₃ , wherein each R ^{6 is} independently selected from the group consisting of: H, substituted or unsubstituted alkyl , substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heterocycloalkyl, and substituted or unsubstituted heterocycloalkylene. In one embodiment of the invention, L is NH ₃ or a substituted or unsubstituted mono- or diaminoalkane, for example substituted or unsubstituted ethylenediamine.

In the explosive metal complexes each anion X may independently selected from the group consisting of F ^-, Cl ^-, Br ^-, I ^-, CN ^-, OCN ^-, NCO ^-, SCN ^-, NCS ^-, NO ₂ ^-, NO 3 ^-, SO ₄ ^2-, HSO ₄ ^-, HPO ₄ ^2-, H2PO ₄ ^-, PO ₄ ^3-, N ₃ ^-, CO ₃ ^2-, ClO ₄ ^-, HC _O3 ^-, HSO ₃ ^- and SO ₃ ^2- is selected become. n is an integer; depending on the metal, n is a number from 0 to 5, and ≤ (h - m), to take into account the h ligand binding sites of the metal ion and to ensure that the metal complex of the formula [ML _m X _n ] carries a net positive charge. In certain embodiments of the invention n is 1, 2 or 3. Depending on the metal, h can be an integer of 1-8, for example 2, 4, 6 or 8. In one embodiment of the invention, X is selected from the group consisting of NO ₂ ^- , NO ₃ ^- and N ₃ ^- .

The NO ₂ ^- anions in the complex compounds can be bound to the metal both via oxygen (nitrito complexes) and via the nitrogen (nitro complexes).

The invention further includes all known isomers of the complex metal cations described herein, such as cis and trans isomers in derivatives having two anionic ligands X.

In one embodiment, the cationic portion of the explosive metal complexes having the formula [ML _m X _n ] ^{p + is} selected from the group consisting of cationic complexes of the transition metal M with NH ₃ and N ₃ ^- , NH ₃ and NO ₂ ^- , ethylenediamine and N ₃ ^- , or ethylenediamine and NO ₂ ^- . These complexes have the general formula [M (NH ₃ ) _b (N ₃ ) _c ] ^{d +} , [M (NH ₃ ) _b (NO ₂ ) _c ] ^{d +} , [M (NH ₂ - (CH ₂ ) ₂ -NH ₂ ) _b (N ₃ ) _c ] ^{d +} or [M (NH ₂ - (CH ₂ ) ₂ -NH ₂ ) _b (NO ₂ ) _c ] ^{d +} , where b, c and d are both integers and at least 1 and depending on the ligand binding sites of the metal are selected. In one embodiment, the metal is a trivalent metal having 6 complex binding sites, such as. B. Co. Exemplary cationic complexes are [Co (NH ₃ ) ₅ N ₃ ] ²⁺ , [Co (NH ₃ ) ₄ (N ₃ ) ₂ ] ⁺ , [Co (NH ₃ ) ₅ NO ₂ ] ²⁺ , [ Co (NH ₃ ) ₄ (NO ₂ ) ₂ ] ⁺ , [Co (NH ₃ ) ₅ NO ₃ ] ²⁺ , [Co (NH ₃ ) ₄ (NO ₃ ) ₂ ] ⁺ , [Co (NH ₂ - (CH ₂ ) ₂ -NH ₂ ) ₂ (N ₃ ) ₂ ] ⁺ , [Co (NH ₂ - (CH ₂ ) ₂ -NH ₂ ) ₂ (NO ₃ ) ₂ ] ⁺ and [Co (NH ₂ - (CH ₂ ) ₂ -NH ₂ ) ₂ (NO ₂ ) ₂ ] +.

In various embodiments, R ^{1 is} -NO ₂ (5-nitrotetrazolate; NT) or -NH-NO ₂ (5-nitroaminotetrazolate; NAT). In other embodiments of the invention, R ^{1 is} -N = NR ⁴ and R ⁴ is selected from the group consisting of tetrazolate (-CN ₄ ^- ) (5,5'-azotetrazolate; AZT) and -NR ⁵ where R ^{5 is} tetrazolate (-CN ₄ ^- ) (5-diazoamidotetrazolate; DAAT). The structural formulas of the anions 5-nitrotetrazolate, 5-nitroaminotetrazolate, 5,5'-azotetrazolate, and 5-diazoamidotetrazolate are in 1 shown.

In certain embodiments, therefore, complexes of the above-mentioned cationic metal complexes with NT, NAT, AZT and / or DAAT are included.

The present invention includes inter alia the following complexes:
[M (NH ₃ ) _b (N ₃ ) _c ] (5,5'-azotetrazolate);
[M (NH ₃ ) _b (N ₃ ) _c ] (5-nitrotetrazolate) ₂ ;
[M (NH ₃ ) _b (N ₃ ) _c ] (5-nitroaminotetrazolate) ₂ ;
[M (NH ₃ ) _b (N ₃ ) _c ] (5-nitrotetrazolate);
[M (NH ₃ ) _b (N ₃ ) _c ] (5-nitroaminotetrazolate);
[M (NH ₃ ) _b (NO ₂ ) _c ] (5,5'-azotetrazolate);
[M (NH ₃ ) _b (NO ₂ ) _c ] (5-nitrotetrazolate) ₂ ;
[M (NH ₃ ) _b (NO ₂ ) _c ] (5-nitroaminotetrazolate) ₂ ;
[M (NH ₃ ) _b (NO ₂ ) _c ] (5-nitrotetrazolate); and
[M (NH ₃ ) _b (NO ₂ ) _c ] (5-nitroaminotetrazolate),
where b + c = h (h = number of ligand-binding sites of the metal) and wherein b and c are chosen such that the total net charge of the complex is zero.

Exemplary are the following cobalt complexes:
[Co (NH ₃ ) ₅ N ₃ ] (5,5'-azotetrazolate);
[Co (NH ₃ ) ₅ N ₃ ] (5-nitrotetrazolate) ₂ ;
[Co (NH ₃ ) ₅ N ₃ ] (5-nitroaminotetrazolate) ₂ ;
[Co (NH ₃ ) ₄ (N ₃ ) ₂ ] ₂ (5,5'-azotetrazolate);
[Co (NH ₃ ) ₄ (N ₃ ) ₂ ] (5-nitrotetrazolate);
[Co (NH ₃ ) ₄ (N ₃ ) ₂ ] (5-nitroaminotetrazolate);
[Co (NH ₃ ) ₅ NO ₂ ] (5,5'-azotetrazolate);
[Co (NH ₃ ) ₅ NO ₂ ] (5-nitrotetrazolate) 2;
[Co (NH ₃ ) ₅ NO ₂ ] (5-nitroaminotetrazolate) ₂ ;
[Co (NH ₃ ) ₄ (NO ₂ ) ₂ ] ₂ (5,5'-azotetrazolate);
[Co (NH ₃ ) ₄ (NO ₂ ) ₂ ] (5-nitrotetrazolate); and
[Co (NH _{3) 4} (NO _{2) 2]} (5-Nitroaminotetrazolat).

In the complexes of the present invention, q and r are selected such that the net charge of the complex is zero.

Also described herein are C- and N-substituted derivatives of the above tetrazole-type nitrogen-containing anions.

Described herein is further an igniter composition containing an initiating explosive selected from the group consisting of the listed explosive metal complexes, as well as styrenic acid or its transition metal compounds, metal nitrotetrazolates such as iron nitrotetrazolate, sodium nitrotetrazolate and copper nitrotetrazolate, metal azotetrazolates such as Iron azotetrazolate, sodium azotetrazolate and copper azotetrazolate, and mixtures thereof. The ignition means is preferably lead-free and / or barium-free. The metal in the azotetrazolates or nitrotetrazolates may be, for example, an alkali or alkaline earth metal or a transition metal.

In various embodiments of the primer, it contains one or more further constituents selected, for example, from the group consisting of further priming explosives, sensitizers, friction agents, oxidants, reducing agents, auxiliaries, binders and secondary explosives.

In one embodiment, the ignition agent contains a sensitizer, such as tetracene. Alternatively, diazodinitrophenol (DDNP) or a mixture of said sensitizers can be used. The proportion of these sensitizers based on the total weight of the ignition mixture may be between 2-40% by weight, preferably 2-15% by weight.

Suitable friction agents include, but are not limited to, glass beads, glass beads, glass powder, calcium silicide, coke powder, boron particles, and mixtures thereof. The proportion of the friction agent in the ignition agent may be from 25 to 60% by weight, preferably from 20 to 50% by weight, based on the total weight of the ignition agent.

Exemplary oxidizers which may be used for the primer / primer mixtures include, but are not limited to, metal oxides, including the oxides of copper, zinc, bismuth, iron, manganese, tin, vanadium and molybdenum, metal peroxides, including zinc peroxide and calcium peroxide. Salts, including salts of inorganic oxygen-containing acids, including saltpetre, the basic nitrate of bismuth, tin and copper or complex salts, including diammonium copper nitrate, and mixtures thereof. The proportion of the oxidizing agent in the total mass of the ignition agent may be 0 to 40 wt .-%, for example 1-20 wt .-%.

Exemplary reducing agents (fuels) include, but are not limited to, metal powders, such as metal powders. As boron, aluminum, cerium, titanium, zirconium, magnesium and / or silicon, metal alloys, such as. B cerium-magnesium, cerium-silicon, titanium-aluminum, aluminum-magnesium and calcium silicide, metal sulfides, such as. For example, antimony sulfide and / or molybdenum sulfide, metal hydrides, such as titanium hydride and zirconium hydride, metal silicates, graphite, activated carbon, carbon black and mixtures thereof. The proportion of the reducing agent may be from 0 to 40% by weight, for example 1-20% by weight, based on the total mixture.

Suitable auxiliaries are, for example, nitrocellulose ball powders, silicates and silica gels, preferably nitrocellulose ball powder.

Binders which can be used in the primer include, but are not limited to, adhesin, cellulose, cellulose derivatives, polyvinyl butyrals, polynitropolyphenylene, polynitrophenyl ethers, Plexigum, gum arabic, dextrins, polyvinyl acetate and copolymers, and mixtures thereof. In one embodiment, the binder is adhesin.

Secondary explosives that can be used in the blends include, but are not limited to, hexogen, octogen, and nitropenta (pentaerythrityl tetranitrate, pentrite, PETN), as well as mixtures thereof. The proportion of secondary explosives in the total mass of the ignition agent may be between 0-30 wt .-%, preferably between 0-15 wt .-%.

Exemplary primer mixtures are (% data are wt .-% based on the total weight of the mixture): ignition mixture 1 Pentaammine (azido) cobalt (III) azotetrazolate 50% tetracene 10% glass powder 40% Ignition mixture 2 Eisennitrotetrazolat 48% tetracene 5% glass powder 47% Ignition mixture 3 Pentaammine (azido) cobalt (III) azotetrazolate 63% tetracene 6% glass powder 31% Ignition mixture 4 tetracene 4% copper nitrate 30% Natriumnitrotetrazolat 43% glass grit 23% Ignition mixture 5 tetracene 4% styphnic 35% potassium carbonate 35% glass powder 26% Ignition mixture 6 Kupfertrizinat 63% tetracene 6% glass powder 31%

The preparation of the ignition is carried out by known methods, such as kneading the water-wet mixture or sieving the dry mixture. The dosage of the water-moist mass can be done, for example, by brushing the perforated plates, by dispensing or by extrusion.

• a) im trockenen Zustand
• b) im trockenen und feuchten Zustand
• c) im feuchten Zustand
• d) im vor gemischten trocken Zustand zur späteren Aktivierung

Furthermore, in the production of explosive articles comprising the described ignition means (eg igniter set in cartridges), the required materials (explosive, oxidizing agent, reducing agent, sensitizer) may be processed during processing and loading as follows

• a) in the dry state
• b) in dry and moist condition
• c) in the wet state
• d) in pre-mixed dry state for later activation

In one embodiment, a predetermined amount of a substantially dry, powdery, relatively insensitive premix containing at least two materials in predetermined proportions is combined so that the components react with each other in the presence of a liquid reaction medium to form the primary explosive, and the ignition composition thereafter dried a certain amount of time. It is within the routine skill of one of ordinary skill in the art to adjust the proportions of the particular ignition mixture with respect to the requirement of the explosive articles.

• (i) Umsetzen eines Metall-Komplexsalzes der Formel [ML_mX_n]_vA_w mit einem stickstoffhaltigen, energiereichen Salz der Formel II
  
  wobei M ein Metall ist, das ausgewählt wird aus den Übergangsmetallen der Gruppen 3–12 des IUPAC-Periodensystems, L ein Neutralligand ist; X ein Anion ist; A ein Anion ist; N ein Kation ist; R¹ -NR²R³ oder -N=N-R⁴ ist, R² und R³ unabhängig voneinander ausgewählt werden aus der Gruppe bestehend aus H, O, NO₂, substituiertem oder unsubstituiertem Alkyl, substituiertem oder unsubstituiertem Alkenyl und substituiertem oder unsubstituiertem Alkinyl, wobei, wenn substituiert, einer oder mehrere Substituenten vorhanden sind, die ausgewählt werden aus der Gruppe bestehend aus Amino, Carbonyl und Hydroxyl; R⁴ ausgewählt wird aus der Gruppe bestehend aus H, substituiertem oder unsubstituiertem Alkyl, substituiertem oder unsubstituiertem Alkenyl, substituiertem oder unsubstituiertem Alkinyl, substituiertem oder unsubstituiertem Aryl, substituiertem oder unsubstituiertem Heteroaryl und -NR⁵, wobei, wenn substituiert, einer oder mehrere Substituenten vorhanden sind, die ausgewählt werden aus der Gruppe bestehend aus Amino, Carbonyl und Hydroxyl; R⁵ ausgewählt wird aus der Gruppe bestehend aus H, Amino, substituiertem oder unsubstituiertem Alkyl, substituiertem oder unsubstituiertem Alkenyl, substituiertem oder unsubstituiertem Alkinyl, substituiertem oder unsubstituiertem Aryl und substituiertem oder unsubstituiertem Heteroaryl, wobei, wenn substituiert, einer oder mehrere Substituenten vorhanden sind, die ausgewählt werden aus der Gruppe bestehend aus Amino, Imino, Carbonyl und Hydroxyl; m eine ganze Zahl von 0 bis 6 ist; n eine ganze Zahl von 0 bis 5 ist, wobei n ≤ (h – m) ist und wobei n und m nicht beide 0 sind; h die Anzahl der möglichen Liganden des Metalls ist; und s, t, u, v und w jeweils eine ganze Zahl von 1 bis 3 sind; in einem geeigneten Lösungsmittel um einen explosiven Metall-Komplex zu bilden; und
• (ii) Isolieren des explosiven Metall-Komplexes.

Also described herein are metathesis reactions to represent the explosive metal complexes. A process for producing a cobalt (III) complex comprises:

• (i) reacting a metal complex salt of the formula [ML _m X _n ] _v A _w with a nitrogen-containing, high-energy salt of the formula II
  
  wherein M is a metal selected from transition metals of Groups 3-12 of the IUPAC Periodic Table, L is a neutral ligand; X is an anion; A is an anion; N is a cation; R ^{1 is} -NR ² R ³ or -N = NR ⁴ , R ² and R ^{3 are} independently selected from the group consisting of H, O, NO ₂ , substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl and substituted or unsubstituted alkynyl wherein, when substituted, there are one or more substituents selected from the group consisting of amino, carbonyl and hydroxyl; R ^{4 is} selected from the group consisting of H, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and -NR ⁵ , wherein when substituted, one or more substituents are present are selected from the group consisting of amino, carbonyl and hydroxyl; R ^{5 is} selected from the group consisting of H, amino, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, wherein when substituted, one or more substituents are present, which are selected from the group consisting of amino, imino, carbonyl and hydroxyl; m is an integer from 0 to 6; n is an integer from 0 to 5, where n ≤ (h-m) and where n and m are not both 0; h is the number of possible ligands of the metal; and s, t, u, v and w are each an integer of 1 to 3; in a suitable solvent to form an explosive metal complex; and
• (ii) isolating the explosive metal complex.

Here, M, L, X, m, n, h, s, t, u, v, w, and R ¹ -R ^{5 are} as defined above for the metal complexes. N is a metallic cation, such as an alkali, alkaline earth or transition metal cation, such as. B. Na, Mg, K, Ca or Al, or is defined as M. Alternatively, N may also be an organic cation or, for example, ammonium. A is an anion, for example defined as X.

Also described herein are metathesis reactions between the appropriate metal complex precursors and the appropriate salts of the nitrogen-containing, high-energy anions in water as the solvent. Alternatively, however, it is also possible to use polar organic solvents, such as, for example, DMF or DMSO, as well as mixtures of these solvents with water.

The reactions described herein can be carried out in such a way that the metal complexes crystallize out of the reaction mixture directly in pure form. This can be achieved, for example, by working in concentrated aqueous solutions.

Isolation of the explosive metal complexes can be readily accomplished by known techniques such as filtration or centrifugation, washing with water or suitable organic solvents such as alcohol, acetone or ether, followed by drying in air or in vacuo. The explosive metal complexes usually accumulate as yellow, orange, red or violet crystalline solids. The characterization can be done for example by elemental analysis, IR spectroscopy, and single-crystal X-ray structure analysis.

In the processes, the starting material used is a salt of the metal complex cation, counteranion A being selected from organic and inorganic anions. Here, A is an inorganic anion, and is selected from the group consisting of F ^-, Cl ^-, Br ^-, I ^-, CN ^-, OCN ^-, NCO ^-, SCN ^-, NCS ^-, NO ₂ ^-, NO ₃ ^-, SO ₄ ^2- , HSO ₄ ^- , HPO ₄ ^2- , H ₂ PO ₄ ^- , PO ₄ ^3- , N ₃ ^- , CO ₃ ^2- , ClO ₄ ^- , HCO ₃ ^- , HSO ₃ ^- and SO ₃ ^2- selected, preferably A is Cl, N ₃ ^- , ClO ₄ ^- or NO ₃ ^- .

The preparation process also uses a salt of the nitrogen-containing, high-energy tetrazole-based anions. In this salt, the cation N may be an organic or inorganic cation. Examples of suitable cations are metal ions, unsubstituted or substituted ammonium, unsubstituted or substituted hydrazinium, unsubstituted or substituted guanidinium, unsubstituted or substituted aminoguanidinium, unsubstituted or substituted phosphonium and unsubstituted or substituted arsonium. The metal ions may be alkali metal ions, alkaline earth metal ions, transition metal ions, Group 3 and 13 metal ions, and lanthanide ions. The substituents may be one or more selected from C ₁ -C ₁₀ alkyl, alkenyl or alkynyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₄ aryl, a 5-10 membered heteroaryl ring in the formula 1 to 4 ring atoms are independently nitrogen, oxygen or sulfur, a 5-10 membered heteroalicyclic ring in which 1 to 3 ring atoms are independently nitrogen, oxygen or sulfur, hydroxy, C ₁ -C ₁₀ alkoxy, C ₃ -C ₈ cycloalkoxy, aryloxy , Mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amide, N-amide, C-carboxy, O-carboxy, nitro, silyl , Sulfinyl, sulfonyl, amino and -NR ⁷ R ⁸ wherein R ⁷ and R ^{8 are} independently hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₄ aryl, carbonyl, acetyl, sulfonyl or amino , or R ⁷ and R ⁸ together with the nitrogen atom to which they are attached form a five- or six-membered heteroalicyclic ring. In a particular embodiment, the substituent (s) are / are selected from organic substituents, preferably C ₁ -C ₁₀ alkyl, alkenyl and alkynyl.

In a further aspect, the invention relates to the use of an explosive metal complex according to the invention as initial explosive. Such initial explosive can be used, for example, in fuel, fuel and Zündsätzen.

Finally, the invention is also directed to the use of the ignition means according to the invention as an explosive, propellant, fuel or Zündsatz. In particular, the primer / primer mixtures of the invention or the explosive metal complexes of the invention may be used in various explosive articles, such as primer sets in rimfire, boxer and Berdan ignitions of cartridges of any caliber.

EXAMPLES

Other embodiments and methods of making metal complexes are included in the claims and examples. The following examples serve to illustrate the invention, but the invention is not limited to these specific embodiments.

Example 1: General procedure for the preparation of complex metal azotetrazolates, nitrotetrazolates and nitroaminotetrazolates

To prepare the complex metal azotetrazolates, nitrotetrazolates and nitroaminotetrazolates, the corresponding starting compounds are dissolved with slight heat and combined with stirring. Thereafter, the reaction solution is left to crystallize. The resulting product is then filtered off and washed with a little water and acetone. To increase the yield, the filtrate is further concentrated.

Example 2: Preparation of pentaammine-azido-cobalt (III) azotetrazolate

500 g (1.945 mol) of pentaammine-azido-cobalt (III) chloride are dissolved in water with gentle heating and mixed with stirring with a concentrated aqueous solution of 583 g of sodium azotetrazolate. After only one day violet, rod-shaped crystals crystallize from the deep purple solution at room temperature. The resulting crystals are filtered off and washed with water. To increase the yield, the filtrate is concentrated and the resulting crystals are filtered off again and washed with cold water.

Example 3: Preparation of tetraammine dinitro cobalt (III) azotetrazolate

500 g (1.96 mol) of tetraammine dinitro cobalt (III) chloride are dissolved in water with gentle heating. To this, 294 g of previously dissolved sodium azotetrazolate are added with stirring. After only a few minutes, the orange product will fail. It is then washed with water, isolated by filtration and dried in air.

Example 4: Preparation of tetraammine dinitro cobalt (III) nitrotetrazolate

500 g (1.96 mol) of tetraammine dinitro cobalt (III) chloride are dissolved in water with gentle heating. With stirring, 268 g of dissolved sodium nitrotetrazolate are added. The reaction solution is stirred with slight heat for 2 h. After about 2 days, orange cuboid crystals precipitate. These are filtered off, washed with water and dried in air.

Example 5: Single-crystal X-ray structure analysis

Selected members of the explosive metal complexes of the invention were structurally confirmed by single crystal X-ray analysis. 2 shows a micrograph of the rod-shaped single crystals of the compound of the invention [Co (NH ₃ ) ₅ N ₃ ] (AZT). The molecular structure of [Co (NH ₃ ) ₅ N ₃ ] (AZT) is in 3 shown.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 4034645 A1 [0004]
• EP 0440873 A2 [0013]
• US 4674409A [0013]
• US 4608102 A [0014]
• US Pat. No. 4,363,679 A [0014]
• FR 2628735 B1 [0014]
• US 5516377A [0014]

Cited non-patent literature

• B. Halford: "Pyrotechnics for the Planet," Chemical & Engineering News 2008, 86, Issue 26, pp. 14-18. [0004]
• TM Klapötke et al .: "[N₂H₅] + ₂ [N₄C-NN-CN₄] ²-A New High-Nitrogen High-Energetic Material", Inorg. Chem. 2001, 40, 3570-3575 [0004]
• J. Thiele: "On Azo and Hydrazo Compounds of Tetrazole," Liebigs Ann. Chem. 1898, 303, 57-75 [0004]
• A. Yu. Zhilin et al .: "Synthesis of a high-energy-capacity compound, tetraammine-cis-bis (nitro-2H-tetrazolato-N 2) cobalt (III) perchlorate", Russ. J. Appl. Chem. 2001, 74, 99-102 [0005]
• AV Smirnov et al .: "Synthesis of Cobalt (III) Ammine Complexes as Explosive for Safe Priming Charges", Russ. J. Appl. Chem. 2004, 77, 794-796 [0005]
• MHV Huynh et al .: "Green primary explosive: 5-nitrotetrazolato-N 2 -ferrate hierarchies", Proc. Natl. Acad. Sci. 2006, 103, 10322-10327 [0005]
• TM Klapötke et al .: "Safe 5-nitrotetrazolate anion transfer reagents", Dalton Trans. 2009, 1835 [0007]

Claims (7)

An explosive metal complex according to any one of the formulas: [M (NH ₃ ) _b (N ₃ ) _c ] (5,5'-azotetrazolate); [M (NH ₃ ) _b (N ₃ ) _c ] (5-nitrotetrazolate) ₂ ; [M (NH ₃ ) _b (N ₃ ) _c ] (5-nitroaminotetrazolate) ₂ ; [M (NH ₃ ) _b (N ₃ ) _c ] (5-nitrotetrazolate); [M (NH ₃ ) _b (N ₃ ) _c ] (5-nitroaminotetrazolate); [M (NH ₃ ) _b (NO ₂ ) _c ] (5,5'-azotetrazolate); [M (NH ₃ ) _b (NO ₂ ) _c ] (5-nitrotetrazolate) ₂ ; [M (NH ₃ ) _b (NO ₂ ) _c ] (5-nitroaminotetrazolate) ₂ ; [M (NH ₃ ) _b (NO ₂ ) _c ] (5-nitrotetrazolate); and [M (NH ₃ ) _b (NO ₂ ) _c ] (5-nitroaminotetrazolate) wherein M is a metal selected from transition metals of Groups 3-12 of the IUPAC Periodic Table; b + c = h are h is the number of possible ligands of the metal; c>0; and b and c are chosen so that the total net charge of the complex is zero. Igniter containing an initial explosive selected from the group consisting of: one or more explosive metal complexes according to claim 1. The primer of claim 2, further comprising at least one further constituent selected from the group consisting of initiating explosives, sensitizers, friction agents, oxidizing agents, reducing agents, adjuvants, binders and secondary explosives. The primer of claim 2 or 3, wherein the primer further contains a sensitizer selected from tetracene and diazodinitrophenol. A primer as claimed in any one of claims 2 to 4, wherein the primer is free of lead and / or barium. Use of a metal complex according to claim 1 as initial explosive. Use of an ignition means according to any one of claims 2 to 5 as an explosive, propellant, fuel or Zündsatz.

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