GAS PHASE SYNTHESIS, STRUCTURE, AND DISSOCIATION OF BORON TRIAZIDE
GAS PHASE SYNTHESIS, STRUCTURE, AND DISSOCIATION OF BORON TRIAZIDE
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DOI：
10.1021/j100017a007
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发表时间：
1995-04
期刊：
影响因子：
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通讯作者：
R. L. Mulinax;G. Okin;R. Coombe
中科院分区：
文献类型：
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作者：
R. L. Mulinax;G. Okin;R. Coombe
富氮分子以其储存能量的能力而闻名。最近对这些物种的研究集中在具有极高比例的氮的小分子，如N4，Ng或叠氮化物取代的化合物。1-3本文介绍了硼酰肼化合物的新情况。除了它们储存大量能量的能力之外，这些物种作为氮化硼薄膜的可能前体还具有额外的兴趣。六方氮化硼薄膜和立方氮化硼薄膜作为宽带隙半导体或摩擦学涂层有着重要的应用。4叠氮化硼的发现已有40多年的历史。1954年，Wiberg和Michaud 5通过乙硼烷与HN 3在醚溶液中低温反应合成了三叠氮硼，B（N3）3。反应放出H2，留下B（N3）3，调节条件以产生H2产率，该产率为从3：1化学计量的反应所预期的产率的约95%。这些作者使用类似的方法来生产Al（Ni）3，以及BCNSi和Al（N3）3与NaN3和LiN3的极高能加合物。在1963年，Paetzold6报道了由BCl3与LiN3在CH2Cl2溶液中的反应合成Cl2BN 3。得到的产物为结晶固体，鉴定为三聚二氯硼叠氮化物（BChNsri）。在加热至200 ℃时，该化合物通过从三聚体中损失N2和氯原子迁移而转化为六氯硼唑。Mueller 7在1971年测定了（Cl2BN 3）的晶体结构，结果证实了三聚体结构。1972年，Wiberg和Michaud也对叠氮化二氯硼进行了研究。这些作者从BCI 3与三甲基硅叠氮在CH 2 Cl 2中的反应中产生它。1978年，Dehnicke 9报道了铝、镓和硼的叠氮化物的生成，这些金属的三碘化物与叠氮化碘在苯中反应。他记录了单叠氮化物产物I2MN3的红外光谱，并观察到这些物质的低聚物的形成。已经使用类似的方法产生烷基叠氮化硼。在1966年，Paetzold10通过（CH3）2BBr和三正丁基甲硅烷基叠氮化物的反应生产了（OHhBN，得到了爆炸性液体的产物。最近，从头计算方法已被用来确定（CH 3）2BN 3的结构。有机叠氮化物与卤代硼化合物的类似反应已被有机化学家用于合成式I的杂环化合物。
Nitrogen-rich molecules are well known for their ability to store energy. Recent research on such species has focused on small molecules with extremely high proportions of nitrogen, such as N4, Ng, or azide-substituted compounds. 1-3 In this paper, we present new information aboutazide compounds of boron. Apartfrom their ability to store large amounts of energy, these species hold additional interest as possible precursors for boron nitride thin films. Both hexagonal and cubic BNfilms have many important applications as either wide band gap semiconductors or as tribological coatings. 4 Boron azides have been known for more than forty years. In 1954, Wiberg and Michaud5 synthesized boron triazide, B (N3) 3, by the reaction of diborane with HN3 in an ether solution at low temperature. The reaction evolved H2 to leave B (N3) 3, and the conditions were adjusted to produce an H2 yield approximately 95% of that expected from the 3: 1 stoichiometry of the reaction. These authors used similar methods to produceA1 (N;) 3, as well as extremely energetic adducts of BCNsri and A1 (N3) 3 with NaN3 and L1N3. In 1963, Paetzold6 reported the synthesis of CI2BN3 from the reaction of BCI3 with L1N3 in a CH2CI2 solution. Theproduct was obtained as a crystalline solid identified as trimeric dichloroboron azide,(BChNsri. Upon heating to 200 C, the compound converted to hexachloroborazole by loss of N2 from the trimer and migration of the chlorine atoms. The crystal structure of (CI2BN3) was determined by Mueller7 in 1971, the results confirming the trimeric structure. Dichloroboron azide was also studied by Wiberg and Michaud8 in 1972. These authorsproduced it from the reaction of BCI3 with trimethylsilyl azide in CH2CI2. In 1978, Dehnicke9 reported the generation of azides of aluminum, gallium, and boron from reactions of the triiodides of these metals with iodine azide in benzene. He recorded theinfrared spectra of the monoazide products, I2MN3, and observed the formation of oligimers of these species. Alkylboron azides have been generated using similar methods. In 1966, Paetzold10 produced (OUhBNs from the reaction of (CHs^ BBr and tri-n-butylsilyl azide, obtaining the product as an explosive liquid. Recently, ab initio computationalmethods have been used11 to determine the structure of (CH3) 2BN3. Similar reactions of organic azides with halogenated boron compounds have been used by organic chemists for the synthesis of heterocyclic ring compounds of