Energetic characteristics of transition metal complexes

Wojewódka, A.; Bełzowski, Janusz; Wilk, Z.; Staś, Justyna

doi:10.1016/j.jhazmat.2009.06.104

Cited by 15 publications

(11 citation statements)

References 6 publications

(5 reference statements)

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“…It is interesting to note that the latter coordination compound combines an "oxidizer", NO 3 − , and a "fuel", N 2 H 4 , and this makes it a potential energetic material. In the recent years, [Ni(N 2 H 4 ) 3 ][NO 3 ] 2 was presented as a safer alternative to lead azide Pb(N 3 ) 2 , a widely used primary explosive (Wojewódka & Bełzowski, 2011;Wojewódka, Bełzowski, Wilk, & Stás, 2009). Indeed, [Ni(N 2 H 4 ) 3 ][NO 3 ] 2 is less sensitive to mechanical stimuli like impact and friction (Hariharanath, Chandrabhanu, Rajendran, Ravindran, & Kartha, 2006).…”

Section: Introductionmentioning

confidence: 99%

Inorganic chemistry laboratory experiment on an energetic nickel (II) coordination compound, aimed at third-year undergraduate students

Demirci

Bernaud

2020

Chemistry Teacher International

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This inorganic chemistry laboratory experiment, aimed at third-year undergraduate students, focuses on an energetic coordination compound, tris(hydrazine)nickel(II) nitrate [Ni(N2H4)3][NO3]2. As long as the solid is not subject to mechanical stimuli (impact and friction), it can be safely synthesized and handled. In our laboratory conditions (see supplementary information), the experiment includes synthesis of [Ni(N2H4)3][NO3]2 in two different morphologies, visual inspection of the samples, analysis by IR spectroscopy, checking the crystallinity by powder X-ray diffraction, 3D visualization of the crystal structure by means of a free program, and observation by scanning electron microscopy. In that respect, the experiment, as a whole, introduces students to nickel(II) complexes, coordination compounds, energetic materials, sonochemical and morphology-controlled syntheses, and a 3D visualization program for crystal structures and structural models. This laboratory experiment is also proposed in the form of alternate (light) versions so that it can be adopted in another inorganic chemistry laboratory that may have restrictions in terms of equipment, and in another third-year curriculum.

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Section: Introductionmentioning

confidence: 99%

Inorganic chemistry laboratory experiment on an energetic nickel (II) coordination compound, aimed at third-year undergraduate students

Demirci

Bernaud

2020

Chemistry Teacher International

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“…A renewed interest in these derivatives was observed in the eighties, as new explosives like NHN [tris(hydrazine)nickel(II) nitrate(V)] and HATP [di(3-hydrazino-4-amino-1,2,3-triazole)copper(II) perchlorate] were developed [3][4][5]. Studies in this area continue to this day and have yielded a new generation of these compounds, exhibiting low sensitivity to mechanical stimuli, high energetic parameters [6,7] and susceptibility to stimulation by laser light. These materials can be used as a base in blasting or ignition caps initiated by a laser beam [8,9].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Safety Properties of New Explosive Coordination Compounds

Wojewódka

Bełzowski

2017

Cent. Eur. J. Energ. Mater.

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Abstract:The present paper details the synthesis of new explosive complexes of the DDT type and the investigation of their sensitiveness to friction and impact. Fourteen new compounds, specifically nitrate and perchlorate complexes of various transition block metals with 5-(2,4,6-trinitrophenylamino)tetrazole, commonly called picrylaminotetrazole (PAT), were synthesised. The nitrate complexes were obtained in yields varying between 8.1% and 75.1%, whereas the perchlorate complexes had yields between 24.9% and 67.3%, with yields typically near the upper bound of the given ranges for both classes of complexes and the low yields obtained for [Co(PAT)3](NO3)3 and [Cd(PAT)3](ClO4)3 being the exception rather than the rule. The structures of these compounds were unambiguously established via XRF and IR spectroscopy, as well as via elemental analysis. Detailed analyses of the safety properties of these new materials were performed in terms of their sensitiveness to friction and impact. In general, the obtained compounds present relatively low sensitivity to mechanical stimuli, like friction and impact, with the nitrate complexes of Ni and Zn exhibiting high sensitivity to impact (1-2 Nm). The rest of the investigated compounds show low sensitivity to mechanical stimuli, comparable to classical blasting materials like PETN, RDX or HMX. It should be noted that, in general, the nitrates were more sensitive to mechanical stimuli than their perchlorate analogues.

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“…More importantly, signifi-cant safety issues exist with the use of hydrazine in the presence of transition metals, particularly with heating; many metal-hydrazine complexes are known to be powerful explosives. [12] We have recently demonstrated the feasibility of C À N cross-coupling reactions in continuous flow, [13] and this strategy represents an attractive solution to minimizing the hazards associated with hydrazine/transition metal mixtures. [14,15] Described herein is a mild and potentially scalable method for the direct cross-coupling of aryl chlorides with hydrazine through the use of continuous flow technology [Eq.(3)], and the application of this technology to the rapid construction of a range of heterocyclic scaffolds.We began our investigation by carrying out several smallscale ( 0.20 mmol) batch experiments to identify suitable reaction conditions; the cross-coupling reaction of 4-chlorotoluene and a commercially available 1.0 m solution of hydrazine in THF (2.0 equiv) was selected for optimization (Table 1).…”

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Mild and Rapid Pd‐Catalyzed Cross‐Coupling with Hydrazine in Continuous Flow: Application to the Synthesis of Functionalized Heterocycles

2013

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Functionalized arylhydrazines are of widespread importance as intermediates in the syntheses of nitrogen-containing heterocycles. [1] In this regard, indoles, [1,2] arylpyrazoles/pyrazolones, [1,3] and aryltriazoles, [1,4] among others, [1] can be efficiently generated from arylhydrazines. These heterocyclic motifs are prevalent structural elements in numerous compounds of significant biological/medicinal value. [5] Among current strategies to generate arylhydrazines, nucleophilic aromatic substitution to an aryl halide (ArX) [6] or diazotization of an aniline followed by reduction of the diazonium salt [7] have long been preparative methods of choice [Eq. (1)]. However, the former method typically requires an arene activated by electron-withdrawing groups, while the diazotization/reduction sequence is redox-exhaustive and involves the generation of unstable diazonium intermediates.Modern cross-coupling technology has provided chemists with powerful tools to construct carbon-nitrogen bonds, [8] and thus presents an alternative method of synthesizing aryl hydrazines. [9] Accordingly, several such cross-coupling strategies have been reported utilizing hydrazine equivalents [10] such as benzophenone hydrazone [Eq. (2)].[10a-f] The only example of direct CÀN cross-coupling with hydrazine was recently reported by Stradiotto et al. [11] While this method represented a notable advance, the reactions were set up in a nitrogen-filled glovebox and required relatively high catalyst loading (3-10 mol % Pd). More importantly, signifi-cant safety issues exist with the use of hydrazine in the presence of transition metals, particularly with heating; many metal-hydrazine complexes are known to be powerful explosives. [12] We have recently demonstrated the feasibility of C À N cross-coupling reactions in continuous flow, [13] and this strategy represents an attractive solution to minimizing the hazards associated with hydrazine/transition metal mixtures. [14,15] Described herein is a mild and potentially scalable method for the direct cross-coupling of aryl chlorides with hydrazine through the use of continuous flow technology [Eq. (3)], and the application of this technology to the rapid construction of a range of heterocyclic scaffolds.We began our investigation by carrying out several smallscale ( 0.20 mmol) batch experiments to identify suitable reaction conditions; the cross-coupling reaction of 4-chlorotoluene and a commercially available 1.0 m solution of hydrazine in THF (2.0 equiv) was selected for optimization (Table 1). A screen of precatalysts [16] revealed tBuXPhos (L2) and BrettPhos (L3) as efficient ligands in promoting the desired monoarylation of hydrazine with 3 mol % catalyst loading at 60 8C for 1 h. Under these conditions, 4-tolylhydrazine 1 was formed in high yield with high selectivity over diarylated products 2 and 3 (entries 2-4). [17,18] We subsequently found that the BrettPhos-based catalyst was extremely active as it provided 1 in 84 % yield with 1.2 equiv of hydrazine at room temperature in only 3 min...

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Energetic characteristics of transition metal complexes

Cited by 15 publications

References 6 publications

Inorganic chemistry laboratory experiment on an energetic nickel (II) coordination compound, aimed at third-year undergraduate students

Inorganic chemistry laboratory experiment on an energetic nickel (II) coordination compound, aimed at third-year undergraduate students

Synthesis and Safety Properties of New Explosive Coordination Compounds

Mild and Rapid Pd‐Catalyzed Cross‐Coupling with Hydrazine in Continuous Flow: Application to the Synthesis of Functionalized Heterocycles

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