Binary pnictogen azides-an experimental and theoretical study: [As(N _3) _4] ~-, [Sb(N _3) _4] ~-, and [Bi(N _3) _5(dmso)] ~(2-)

Schulz A.; Villinger A.

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Binary pnictogen azides-an experimental and theoretical study: [As(N _3) _4] ~-, [Sb(N _3) _4] ~-, and [Bi(N _3) _5(dmso)] ~(2-)

机译：叠氮叠氮化物的实验和理论研究：[As（N _3）_4]〜-，[Sb（N _3）_4]〜-和[Bi（N _3）_5（dmso）]〜（2-）

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[PPh _4][EI _4] (E=As, Sb, Bi) salts were reacted with four and five equivalents of AgN _3 to form tetraazidopnictates and pentaazidopnictates of the type [PPh _4][E(N _3) _4] and [PPh _4] _2[E(N _3) _5], respectively. The synthesis of [PPh _4][P(N _3) _4] was also attempted from the reaction of P(N _3) _3 with [PPh _4]N _3, but it yielded only the starting materials. Herein, we report the synthesis and structure elucidation of [PPh _4][E(N _3)] _4 (E=As, Sb) and pentaazidobismuthate, stabilized as the dimethyl sulfoxide (DMSO) anion adduct, [PPh _4] _2[Bi(N _3) _5(dmso)]. Successive anion formation along the series E(N _3) _3+nN _3 ~- (n=1-3) and E(N _3) _5+N _3 ~- was studied by density functional theory. In the pnic of time: The synthesis and structures of the hitherto unknown tetraazidoarsenate and tetraazidoantimonate, as well as the pentaazidobismuthate (stabilized as its DMSO adduct) are discussed along with theoretical details on binary pnictogen species in the oxidation states +III and +V.

机译：[PPh _4] [EI _4]（E = As，Sb，Bi）盐与四和五当量的AgN _3反应，形成[PPh _4] [E（N _3）_4]和[ PPh _4] _2 [E（N _3）_5]。还从P（N _3）_3与[PPh _4] N _3的反应中尝试了[PPh _4] [P（N _3）_4]的合成，但仅产生了起始原料。在这里，我们报告[PPh _4] [E（N _3）] _4（E = As，Sb）和五叠氮铋铋酸盐的合成和结构解析，它们稳定为二甲亚砜（DMSO）阴离子加合物[PPh _4] _2 [Bi （N _3）_5（dmso）]。利用密度泛函理论研究了沿E（N _3）_3 + nN _3〜-（n = 1-3）和E（N _3）_5 + N _3〜-系列的连续阴离子形成。在时间上，讨论了迄今未知的四叠氮砷酸盐和四叠氮锑酸盐以及五叠氮铋铋酸盐（稳定为其DMSO加合物）的合成和结构，以及关于氧化态+ III和+ V的二元光气物种的理论细节。

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《Chemistry: A European journal》 |2012年第10期|共10页
作者
Schulz A.; Villinger A.;
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正文语种 eng
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arsenic; azides; bismuth; pnictogen; thermochemistry;

机译：砷;叠氮化物;铋;光气;热化学;

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机译：叠氮叠氮化物的实验和理论研究：[As（N _3）_4]〜-，[Sb（N _3）_4]〜-和[Bi（N _3）_5（dmso）]〜（2-）
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Binary pnictogen azides-an experimental and theoretical study: [As(N _3) _4] ~-, [Sb(N _3) _4] ~-, and [Bi(N _3) _5(dmso)] ~(2-)

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