Photoisomerization of 1,2-Dihydro-1,2-Azaborine: A Matrix Isolation Study
Photoisomerization of 1,2-Dihydro-1,2-Azaborine: A Matrix Isolation Study
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DOI：
10.1002/anie.201203546
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发表时间：
2012-01-01
影响因子：
16.6
通讯作者：
Bettinger, Holger F.
中科院分区：
文献类型：
--
作者：
Brough, Sarah A.;Lamm, Ashley N.;Bettinger, Holger F.
硼氮杂环化合物由于其作为配体的广泛应用[1]以及在有机光学和电子器件中的潜在应用，近年来受到了广泛的关注。[2]1，2-二氢-1，2-氮杂硼杂环化合物是六元杂环，与苯等电子，其中C= C单元被B= N单元取代。[3]这些化合物最初由Dewar和白色在20世纪60年代报道[4]，在过去的十年中，Ashe等人探索了取代的1，2-二氢-1，2-氮杂硼杂环[1c，5]的例子以及它们在配位化学中的潜力。[6]2009年，对1，2-二氢-1，2-氮杂硼杂环的化学[1c，7]性质[8]和应用[9]的重新关注导致了母体1，2-二氢-1，2-氮杂硼杂环（1）（一种苯电子等排体）的合成和分离。[10]不同的分析，包括反应量热法，化学衍生和磁性标准，得出结论，1的芳香特性是苯和环硼氮烷之间的中间体，苯的无机等电子相对物。[6c自2009年1的合成以来，它所进行的化学类型的实例出现在文献中。例如，1在温和的反应条件下容易发生亲核芳族取代反应[12]，并且Liu和同事最近合成了阳离子1，2-氮杂硼杂环。[13]据我们所知，1，2-二氢-1，2-氮杂硼杂环的光化学研究还从未有人进行过。
Boron-nitrogen heterocycles have received much interest in recent years, due to their wide applications as ligands [1] and potential use in organic optical and electronic devices.[2] 1, 2-Dihydro-1, 2-azaborine compounds are six membered heterocycles and are isoelectronic to benzene, with a C= C unit replaced by a B= N unit.[3] These compounds were initially reported in the 1960’s by Dewar and White,[4] and during the last ten years, examples of substituted 1, 2-dihydro-1, 2-azaborines [1c, 5] as well as their potential in coordination chemistry were explored by Ashe et al.[6] Renewed interest in 1, 2-dihydro-1, 2-azaborine chemistry,[1c, 7] properties [8] and applications [9] led to the synthesis and isolation of parent 1, 2-dihydro-1, 2-azaborine (1), a benzene isostere, in 2009.[10]Varying analyses, including reaction calorimetry, chemical derivatization, and magnetic criteria, concluded that the aromatic character of 1 is intermediate of that between benzene and borazine, the inorganic isoelectronic relative of benzene.[6c, 10, 11] Since the synthesis of 1 in 2009, examples of the types of chemistry it performs are appearing in the literature. For example, 1 readily undergoes nucleophilic aromatic substitution reactions under mild reaction conditions [12] and cationic 1, 2-azaborines have recently been synthesized by Liu and co-workers.[13] To the best of our knowledge, the photochemistry of 1, 2-dihydro-1, 2-azaborines has never been investigated.