碳龙配体修饰及轴手性碳龙配合物的合成

本课题组报道了一系列金属位于桥位，并且含有双五元环骨架的金属 杂芳香配合物，这一系列金属杂芳香配合物被称为“碳龙配合物”，其化学 被命名为“碳龙化学”。结构决定性能，性能决定应用，碳龙配合物独特的 结构，决定了其具有独特性能。大多数碳龙配合物具有强而宽的吸收光谱， 在吸收光后，除了常规地将其转化为光、电、热之外，有时候还会发生超 声波，甚至部分碳龙化合物具有 AIE 效应。除此之外，碳龙配合物还能应 用于均相催化。 膦配体能与金属配位形成高催化活性的配合物，所以膦配体已被广泛 应用于有机合成；同时膦配体也会影响配合物光电活性。很多碳龙配合物 的金属中心含有一个或两个膦配体，为了探究该类配体对碳龙配合物性能 的影响，我们对它们进行了修饰，并测试了产物的光学性质及不对称催化 性能：以锇杂戊搭烯并锇杂喹啉为研究对象，发现不同的膦配体对其紫外 可见吸收光谱有一定的影响；以金属中心手性锇杂环氧丙烯并锇杂戊搭烯 为研究对象，发现膦配体对其催化(E)-4-羟基-4-甲基-1-苯基戊基-1-烯-3 酮与吲哚的不对称 Michael 加成反应结果影响较大，当膦配体为 P(p OCH3-C6H4)3 时，产率可达 92%，ee 值为 75%，相较于膦配体为 PPh3时 结果有很大提升（产率85%，ee值35%）。 轴手性骨架是许多药物分子和天然产物的重要结构单元，并且被广泛 应用于不对称催化。现有的轴手性骨架基本不含过渡金属。我们通过设计 合适的多炔碳链，运用手性传递的策略，将多炔碳链的碳中心手性转移到 碳龙配合物的轴上：使用ee值大于99%的多炔碳链，最高可制备 ee值为 93%的轴手性碳龙配合物。我们不仅合成了轴手性金属锇碳龙配合物，还 合成了轴手性金属铱碳龙配合物。这类特殊轴手性碳龙配合物的性能有待 进一步探究。

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