The First Structural Characterization of a Binary P–N Molecule: The Highly Energetic Compound P<sub>3</sub>N<sub>21</sub>

Göbel, Michael; Karaghiosoff, Konstantin; Klapötke, Thomas M.

doi:10.1002/anie.200601670

Cited by 43 publications

(25 citation statements)

References 16 publications

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“…9 It can be seen that both the calculated lattice constants and the internal structure parameters of P 3 N 21 assigned by the bond lengths and bond angles are close to the corresponding experimental data as shown in Table 1. These comparisons confirm that our computational parameters are reasonably satisfactory.…”

Section: Bulk Propertiessupporting

confidence: 72%

“…It is not negligible that only five atoms are observed in the six-membered ring in Figure 2a, i.e., there is a lack of one nitrogen atom, suggesting that the six-membered ring is not absolutely planar, which agrees well with the reference. 9 It also can be seen from Figure 2a that there is no charge density in the intermolecular regions in the plane containing the three phosphorus atoms, indicating that the intermolecular interaction between the neighboring molecules along this direction in the bulk is very weak. In contrast, Figure 2b shows that a little charge density is overlapped for the azido groups of the neighboring molecules in the plane, thereby, the intermolecular interaction along this direction is stronger.…”

Section: Charge Distributionmentioning

confidence: 86%

“…The six-membered ring is not absolutely planar and takes a slight chair conformation. 9 For the periodic calculation, both high quality basis set and large enough k points should be adopted. Due to the periodicity of the lattice, the calculated orbital energies will depend on the crystal orbital wave vector k. Therefore 260k points were adopted in reciprocal space for the periodic calculation.…”

Section: Computational Detailsmentioning

confidence: 99%

“…The P 3 N 21 compound is extremely sensitive, therefore, the first structural characterization through the single-crystal X-ray diffraction was made until 2006 by Göbel et al 9 In addition, they investigated the IR, Raman, NMR and MS spectroscopy, also DSC and sensitivity properties. The vibrational frequencies were assigned by comparison with the frequencies calculated for a molecule of C 1 point symmetry.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9] For example, the energetic phosphazene compounds without heavy metal elements are environmentally friendly and have very high energy density. In 1954, Grundmann et al 3 first reported the synthesis of P 3 N 21 compound through the reaction of hexachlorophosphazene with sodium azide, but the title compound has only been characterized by elemental analysis.…”

Section: Introductionmentioning

confidence: 99%

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Ab initio Study of Electronic Structure and Properties in Crystalline 1,1,3,3,5,5‐Hexaazidocyclotriphosphazene

Huang

Zhang

Zhang³

et al. 2008

Chin. J. Chem.

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The banding and electronic structures of crystalline 1,1,3,3,5,5-hexaazidocyclotriphosphazene (P 3 N 21 ) have been investigated at DFT-B3LYP/6-31G(d) level. Relaxed crystal structure compares well with experimental data. The energy gap is 5.57 eV, indicating that P 3 N 21 is an insulator. The frontier orbital is mainly formed by atomic orbitals of azido group, so it is the most reactive part of the molecule. The intermolecular interaction is strong along the direction that is nearly perpendicular to the phosphazene ring. The distribution of electrostatic potential is quite uneven, so P 3 N 21 has a very high impact sensitivity. The point charge electrostatic potential is very high between the azido groups of the neighboring molecules, which indicates that the crystal lattice in this position may easily be broken and becomes the explosion center when P 3 N 21 is impacted. The overlap populations of P-N α bonds are much less than those of other bonds, therefore the P-N α bonds first rupture by external stimuli, which agrees well with the experimental study of mass spectrum.

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Section: Bulk Propertiessupporting

confidence: 72%

Section: Charge Distributionmentioning

confidence: 86%

Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Ab initio Study of Electronic Structure and Properties in Crystalline 1,1,3,3,5,5‐Hexaazidocyclotriphosphazene

Huang

Zhang

Zhang³

et al. 2008

Chin. J. Chem.

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Development and Testing of Energetic Materials: The Concept of High Densities Based on the Trinitroethyl Functionality

Göbel

Klapötke

2009

Adv Funct Materials

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212

116

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The development of new energetic materials is an emerging area of materials chemistry facilitated by a worldwide need to replace materials used at present, due to environmental considerations and safety requirements, while at the same time securing high performance. The development of such materials is complex, owing to the fact that several different and apparently mutually exclusive material properties have to be met in order for a new material to become widely accepted. In turn, understanding the basic principles of structure property relationships is highly desirable, as such an understanding would allow for a more rational design process to yield the desired properties. This article covers the trinitroethyl functionality and its potential for the design of next generation energetic materials, and describes relevant aspects of energetic materials chemistry including theoretical calculations capable of reliably predicting material properties. The synthesis, characterization, energetic properties, and structure property relationships of several new promising compounds displaying excellent material properties are reported with respect to different kinds of applications and compared to standard explosives currently used. Based on a review of trinitroethyl‐containing compounds available in the literature, as well as this new contribution, it is observed that high density can generally be obtained in a more targeted manner in energetic materials taking advantage of noncovalent bonding interactions, a prerequisite for the design of next generation energetic materials.

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Isolation of a Carbene‐Stabilized Phosphorus Mononitride and Its Radical Cation (PN^+.)

2010

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In contrast to the inert nature of N 2 , diphosphorus (P 2 )[1] and diarsenic (As 2 ) [2] are only persistent in the gas phase at high temperatures; otherwise, they dimerize to form the stable tetrahedral white phosphorus (P 4 ) and yellow arsenic (As 4 ). Phosphorus mononitride (PN) has attracted a lot of interest, [3] mostly because it is an important component of the interstellar medium and the atmospheres of Jupiter and Saturn. [4] In the laboratory, gaseous PN has been synthesized by pyrolysis of different precursors, and the phosphorus-nitrogen bond length (1.49 ) determined by microwave spectroscopy.[5] In the condensed phase, PN is even more prone to association than P 2 and As 2 . Its dimer, P 2 N 2 , has not yet been detected experimentally, and its trimer has only been observed spectroscopically in a krypton matrix at 40 K. [6] Although the combination of two Group 15 elements does not preclude the isolation of small clusters, as shown by the recent discovery of AsP 3 , [7] the smallest discrete binary PN molecule that has been structurally characterized is P 3 N 21 . [8,9] [11g] only a single report describes the reaction of PN with metal atoms of Group 11 at 10 K.[12] The corresponding complexes have only been characterized by IR spectroscopy, and the description as monomeric PN complexes has been debated. [3d] Recently, it was shown that, just like transition metals, stable singlet carbenes can activate small molecules.[13] They also coordinate main group elements in their zero oxidation state, [14] leading to stable species such as carbodicarbenes (bent allenes) A [15,16] and diatomic silicon B 1 , [17a] germanium B 2 , [17b] phosphorous C 1 , [13e, 18] and arsenic C 2 [19] (Scheme 1). Herein we report the isolation of phosphorus mononitride stabilized by two carbenes. We also describe the one-electron oxidation of PN, which allows the complete characterization of the first isolable PN radical cation.The nitrogen atom was installed by treatment of NHC 1 [20] with bromine, followed by addition of aqueous ammonia. Deprotonation of 2 with nBuLi and addition of phosphorus trichloride afforded compound 3 in 68 % yield. The desired product 5 was then obtained in 88 % yield by reacting 3 with cyclic alkyl amino carbene (CAAC) 4[21] and subsequent reduction with excess magnesium (Scheme 2).Compound 5 is indefinitely stable, even in air at room temperature, both in the solid state and in solution. The 31 P NMR signal (d = + 134.0 ppm) appears at lower field than those of C 1 (d = + 59.4-À73.6 ppm), [18] which is expected because of the difference of electronegativity between nitrogen and phosphorus. Single crystals of 5 melt at 215 8C, and no decomposition was observed by heating a toluene solution under reflux for 24 h. According to the X-ray diffraction study [22] (Figure 1 a), compound 5 has a planar trans-bent geometry (N1-P1-C4 102.788, C1-N1-P1 122.128, C1-N1-P1-C4 torsion angle 179.388). Both the P1ÀC4 (1.719 ) and C1À N1 (1.282 ) bonds are rather short, and the central P À N bond (1.7085 )...

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The First Structural Characterization of a Binary P–N Molecule: The Highly Energetic Compound P₃N₂₁

Cited by 43 publications

References 16 publications

Ab initio Study of Electronic Structure and Properties in Crystalline 1,1,3,3,5,5‐Hexaazidocyclotriphosphazene

Ab initio Study of Electronic Structure and Properties in Crystalline 1,1,3,3,5,5‐Hexaazidocyclotriphosphazene

Development and Testing of Energetic Materials: The Concept of High Densities Based on the Trinitroethyl Functionality

Isolation of a Carbene‐Stabilized Phosphorus Mononitride and Its Radical Cation (PN^+.)

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The First Structural Characterization of a Binary P–N Molecule: The Highly Energetic Compound P3N21

Cited by 43 publications

References 16 publications

Ab initio Study of Electronic Structure and Properties in Crystalline 1,1,3,3,5,5‐Hexaazidocyclotriphosphazene

Ab initio Study of Electronic Structure and Properties in Crystalline 1,1,3,3,5,5‐Hexaazidocyclotriphosphazene

Development and Testing of Energetic Materials: The Concept of High Densities Based on the Trinitroethyl Functionality

Isolation of a Carbene‐Stabilized Phosphorus Mononitride and Its Radical Cation (PN+.)

Contact Info

Product

Resources

About

The First Structural Characterization of a Binary P–N Molecule: The Highly Energetic Compound P₃N₂₁

Isolation of a Carbene‐Stabilized Phosphorus Mononitride and Its Radical Cation (PN^+.)