Ammonium Azide

Frierson, W. J.; Filbert, W. F.

doi:10.1002/9780470132333.ch39

“…[P 4 N 4 (NH) 4 ](NH 3 ) ( 1 ) was obtained by a high‐pressure high‐temperature reaction22–25 at 600 °C and 11 GPa in a Walker‐type multianvil assembly starting from a mixture of ammonium azide NH 4 N 3 26 and P 3 N 5 27 [Eq. (1)].…”

mentioning

confidence: 99%

“…(1)]. Under normal pressure NH 4 N 3 decomposes into NH 3 and HN 3 at 133 °C 26. Above approximately 300 °C highly exothermic explosive decomposition occurs frequently and nitrogen is formed as well [Eq.…”

mentioning

confidence: 99%

A Nitridic Clathrate: P₄N₄(NH)₄(NH₃)

Karau

¹

,

Schnick

²

2006

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In molecular and solid-state chemistry, some phosphorus-and nitrogen-containing compounds exhibit specific similarities and analogies to silicon-oxygen compounds. This resemblance is explained by the isolobal relation between PÀN and SiÀO bonds. [1, 2] Simple examples are phosphorus nitride imide, PN(NH), [3,4] and phosphorus oxide nitride, PON, [5] which are both isoelectronic with silica, SiO 2 . Accordingly, both compounds crystallize in b-cristobalite-analogous network structures and are made up of corner-sharing PX 4 tetrahedra (X = O, N). The ternary nitridophosphates NaPN 2 and LiPN 2 [6][7][8][9] have filled isoelectronic [PN 2 ] À network structures and are structurally related to PON and PN(NH), as they adopt the chalcopyrite structure type. More complex silica analogues are represented by the class of nitridosodalites [10][11][12][13] and related oxonitridosodalites. [14] Recently, we synthesized and identified the first oxonitridic zeolite, [15] namely, Li x H 12ÀxÀy+z [P 12 O y N 24Ày ]X z with X = Cl, Br.[16] The [P 12 O y N 24Ày ] framework of this new framework type (NPO [17] ) contains large 12-ring channels and is solely made up of 3-rings (i.e., rings composed of 12 or 3 corner-sharing tetrahedra, respectively) as fundamental building units (FBUs). [16] The specific topology of the framework type NPO has been identified previously as a possible candidate structure for microporous SiO 2 , [18] but this prediction has not been proven by experiment so far.Besides the diverse and manifold substance class of zeolites [19] and zeosils, [20] another group of microporous solids is formed by clathrasils and clathralites [20,21] (generic term: clathrate). Usually these compounds contain uncharged SiO 2 framework structures of corner-sharing SiO 4 tetrahedra with neutral molecules (or nothing) in their cagelike pores. Herein we report on the first nitridic clathrate [P 4 N 4 (NH) 4 ]-(NH 3 ) (1), which is based on a novel PN(NH) framework structure.[P 4 N 4 (NH) 4 ](NH 3 ) (1) was obtained by a high-pressure high-temperature reaction [22][23][24][25] at 600 8C and 11 GPa in a Walker-type multianvil assembly starting from a mixture of ammonium azide NH 4 N 3 [26] we have employed the multianvil technique for the synthesis and investigation of the high-pressure behavior of silicaanalogous phosphorus nitrides [9,22,25] and recently we synthesized the high-pressure polymorph g-P 3 N 5 .[28] We have frequently used high N 2 partial pressures, generated in situ by thermolysis of azides, in our synthetic approaches to metalcontaining nitridophosphates starting from the respective metal azide and P 3 N 5 . Thereby, phosphorus nitride P 3 N 5 (thermal decomposition > 850 8C at normal pressure [22] ) is prevented from dissociation into the elements [Eq. (2)] at thehigh reaction temperatures [22] above 1000 8C that are usually necessary for the crystallization of the desired metal nitridophosphates.In the current work we utilized the thermolysis of ammonium azide NH 4 N 3 under high pressure and high temperature ...

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“…Under normal pressure NH 4 N 3 decomposes into NH 3 and HN 3 at 133 8C. [26] Above approximately 300 8C highly exothermic explosive decomposition occurs frequently and nitrogen is formed as well [Eq.(3)]. At moderate pressures (ca.…”

mentioning

confidence: 99%

“…[P 4 N 4 (NH) 4 ](NH 3 ) (1) was obtained by a high-pressure high-temperature reaction [22][23][24][25] at 600 8C and 11 GPa in a Walker-type multianvil assembly starting from a mixture of ammonium azide NH 4 N 3 [26] and P 3 N 5 [27] we have employed the multianvil technique for the synthesis and investigation of the high-pressure behavior of silicaanalogous phosphorus nitrides [9,22,25] and recently we synthesized the high-pressure polymorph g-P 3 N 5 . [28] We have frequently used high N 2 partial pressures, generated in situ by thermolysis of azides, in our synthetic approaches to metalcontaining nitridophosphates starting from the respective metal azide and P 3 N 5 .…”

mentioning

confidence: 99%

“…Further experimental and theoretical investigations are planned to shed light on this issue and to further broaden this novel high-pressure approach to hitherto unknown porous structures. Experimental Section P 4 N 4 (NH) 4 (NH 3 ) (1) was synthesized from the starting materials NH 4 N 3 [26] and P 3 N 5 [27] by high-pressure high-temperature synthesis in a similar way as outlined in the literature [22] in a Walker-type multianvil [24,38] module. Octahedra with an edge length of 14 mm (Ceramic Substrates, Isle of Wight) were used, and the sample was placed into a capsule made of hexagonal boron nitride (Henze, Kempten).…”

mentioning

confidence: 99%

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A Nitridic Clathrate: P₄N₄(NH)₄(NH₃)

Karau

¹

,

Schnick

²

2006

View full text Add to dashboard Cite

In molecular and solid-state chemistry, some phosphorus-and nitrogen-containing compounds exhibit specific similarities and analogies to silicon-oxygen compounds. This resemblance is explained by the isolobal relation between PÀN and SiÀO bonds. [1, 2] Simple examples are phosphorus nitride imide, PN(NH), [3,4] and phosphorus oxide nitride, PON, [5] which are both isoelectronic with silica, SiO 2 . Accordingly, both compounds crystallize in b-cristobalite-analogous network structures and are made up of corner-sharing PX 4 tetrahedra (X = O, N). The ternary nitridophosphates NaPN 2 and LiPN 2 [6][7][8][9] have filled isoelectronic [PN 2 ] À network structures and are structurally related to PON and PN(NH), as they adopt the chalcopyrite structure type. More complex silica analogues are represented by the class of nitridosodalites [10][11][12][13] and related oxonitridosodalites. [14] Recently, we synthesized and identified the first oxonitridic zeolite, [15] namely, Li x H 12ÀxÀy+z [P 12 O y N 24Ày ]X z with X = Cl, Br.[16] The [P 12 O y N 24Ày ] framework of this new framework type (NPO [17] ) contains large 12-ring channels and is solely made up of 3-rings (i.e., rings composed of 12 or 3 corner-sharing tetrahedra, respectively) as fundamental building units (FBUs). [16] The specific topology of the framework type NPO has been identified previously as a possible candidate structure for microporous SiO 2 , [18] but this prediction has not been proven by experiment so far.Besides the diverse and manifold substance class of zeolites [19] and zeosils, [20] another group of microporous solids is formed by clathrasils and clathralites [20,21] (generic term: clathrate). Usually these compounds contain uncharged SiO 2 framework structures of corner-sharing SiO 4 tetrahedra with neutral molecules (or nothing) in their cagelike pores. Herein we report on the first nitridic clathrate [P 4 N 4 (NH) 4 ]-(NH 3 ) (1), which is based on a novel PN(NH) framework structure.[P 4 N 4 (NH) 4 ](NH 3 ) (1) was obtained by a high-pressure high-temperature reaction [22][23][24][25] at 600 8C and 11 GPa in a Walker-type multianvil assembly starting from a mixture of ammonium azide NH 4 N 3 [26] we have employed the multianvil technique for the synthesis and investigation of the high-pressure behavior of silicaanalogous phosphorus nitrides [9,22,25] and recently we synthesized the high-pressure polymorph g-P 3 N 5 .[28] We have frequently used high N 2 partial pressures, generated in situ by thermolysis of azides, in our synthetic approaches to metalcontaining nitridophosphates starting from the respective metal azide and P 3 N 5 . Thereby, phosphorus nitride P 3 N 5 (thermal decomposition > 850 8C at normal pressure [22] ) is prevented from dissociation into the elements [Eq. (2)] at thehigh reaction temperatures [22] above 1000 8C that are usually necessary for the crystallization of the desired metal nitridophosphates.In the current work we utilized the thermolysis of ammonium azide NH 4 N 3 under high pressure and high temperature ...

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