金属杂戊搭烯衍生物的官能团化研究

金属杂芳香化学是芳香化学与金属有机化学相结合的化学， 是目前最前沿的研究领域之一。 金属杂芳香化合物是在芳香环中含有金属原子的配合物。 由于过渡金属及其辅助配体种类多， 因此金属杂芳香化合物具有可调控性强、 激发态寿命长等特征， 有广阔的应用前景。 金属杂戊搭烯衍生物是一类结构新颖的金属杂芳香化合物， 但是， 金属杂戊搭烯衍生物的修饰方法仍较少， 这种局限性限制了该类配合物的进一步应用。
本论文希望通过研究铱杂戊搭烯与锇杂戊搭烯衍生物的官能团化方法，合成一系列具有新骨架的碳龙配合物， 为其进一步应用研究奠定基础。从引言开始， 简要介绍了芳香性的概念、 芳香性实验和理论上的判据， 综合文献， 介绍了几类主要的金属杂芳香化合物， 对金属杂芳香化合物中的锇杂戊搭炔与锇杂戊搭烯衍生物(碳龙配合物)做了更详细的介绍， 并且结合以上内容， 简单陈述了论文的设想与目的。 在本论文中，研究了一种“ 一锅法” 合成β-位取代的铱杂戊搭烯衍生物的方法。 通过金属原料、 商业化的有机多炔碳链、 亲核试剂在室温下“ 一锅法” 反应，可生成一系列该类化合物。 其中， 可选择的亲核试剂范围也较广， 多个O 中心、 C 中心和 N 中心的亲核试剂均适用于该类反应。

除此之外， 还研究了一种锇杂戊搭烯衍生物与咔唑衍生物的反应性。 通过含酯基的锇杂戊搭烯衍生物与咔唑衍生物的反应， 可将咔唑骨架引入到锇杂戊搭烯配合物中。 最后， 研究了锇杂戊搭烯并环丁二烯及锇杂戊搭烯并呋喃与四氰基乙烯的扩环反应。 其中锇杂戊搭烯并环丁二烯与四氰基乙烯反应的产物为首例全闭环碳龙配合物； 而锇杂戊搭烯并呋喃与四氰基乙烯反应时， 在不同的溶剂中， 得到不同产物。
综上所述， 本论文研究了三种针对金属杂戊搭烯衍生化的方法， 合成了十九种碳龙配合物， 通过核磁共振 (NMR)， X-Ray 单晶衍射与高分辨质谱 (HRMS)对它们作了充分的表征。 本论文这不仅为后续的碳龙配合物结构的衍生化提供了新思路， 还有望进一步拓宽碳龙配合物在各种领域的应用。
 

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