Mechanism of the Curtius-type rearrangement in the boron series. An ab initio study of the boryinitrene (H2B–N)–iminoborane (HBNH) isomerisation
Mechanism of the Curtius-type rearrangement in the boron series. An ab initio study of the boryinitrene (H2B–N)–iminoborane (HBNH) isomerisation
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硼系列中 Curtius 型重排的机制。硼氮烯 (H2B–N)–亚氨基硼烷 (HBNH) 异构化的从头开始研究。
DOI：
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发表时间：
1987
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影响因子：
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通讯作者：
M. Nguyen
中科院分区：
文献类型：
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作者：
M. Nguyen
H_2BN到HBNH重排模型的从头计算表明，叠氮硼(r2b-N3)生成亚胺硼烷(RBNR)的Curtius型热分解不涉及氮化硼(r2b-N)的中间体，但在光化学条件下，后者可以由叠氮化物的最低三重态形成，不会重排成更稳定的异构体，而是发生典型的反应。
Ab initio calculations on the model H2BN to HBNH rearrangement suggest that the Curtius-type thermolysis of boron azide (R2B–N3) yielding iminoborane (RBNR) does not involve the intermediacy of borylnitrene (R2B–N); under photochemical conditions, the later can, however, be formed from the lowest-lying triplet state of azide and does not rearrange to its more stable isomer but undergoes instead typical reactions.