三并金属杂环戊二烯型碳龙化合物的合成及其在催化氢转移反应中的应用

金属杂环戊二烯是一类重要的金属杂环化合物，碳龙配合物是本课题组开发的一类具有新颖结构和独特性质的金属有机化合物，如果能将金属杂环戊二烯与碳龙配合物结合起来，产生的全新物质将可能具备以上两类物质的性质，对它们的研究有望进一步促进金属有机化学的发展。

首先，本论文利用含有M≡C键的金属杂戊搭炔与碳负离子亲核试剂反应，开发了一种形式上的[3+2]合成金属杂环戊二烯的新方法，以10 % ~ 84 %的产率得到了10例三并金属杂环戊二烯型碳龙化合物。它们的结构通过核磁共振波谱、X射线单晶衍射以及高分辨质谱等方法进行了详细鉴定和分析，更重要的是，反应的关键中间体结构也得到了高分辨质谱的证实，使得我们对该反应历程有了更加深刻的理解和认识。

在此基础上我们进一步探索了所得三并金属杂环戊二烯型碳龙化合物对于氢转移反应的催化效果。对于以醇和伯胺为原料制备仲胺的借氢反应，在最优条件下，可以以40 % ~ 88 %的分离收率得到一系列仲胺产物；对于无受体脱氢偶联制备喹啉衍生物的反应，在最优条件下，同样可以以57 % ~ 95 %的产率得到一系列喹啉衍生物。在反应探索中我们还揭示了催化过程中存在的特殊的“金属-配体”协同催化作用。

Metallacyclopentadienes are an important class of metallocyclic compounds, Carbolong complexes are a series of organometallic compounds with novel structures and unique properties developed by our research group. The amalgamation of metallacyclopentadienes with carbolong complexes could yield new materials that amalgamate the properties of both, potentially spearheading further advancements in organometallic chemistry.

Firstly, this thesis develops a novel method for the formal [3+2] synthesis of metallacyclopentadienes by reacting metallapentalkynes containing a M≡C bond with carbanion nucleophiles, achieving yields from 10% to 84% for ten carbolong complexes with three fused-metallacyclopentadienes . Their structures were detailedly characterized by nuclear magnetic resonance spectroscopy, X-ray single-crystal diffraction, and high-resolution mass spectrometry. More importantly, the structure of one critical reaction intermediate was also confirmed by high-resolution mass spectrometry, providing a deeper understanding and insight into the reaction mechanism.

We further explored the catalytic performance of the obtained carbolong complexes on hydrogen transfer reactions. For the borrowing hydrogen reactions that employ alcohols and primary amines to synthesize secondary amines, optimized conditions enabled the acquisition of a series of secondary amine products with isolated yields from 40% to 88%. Similarly, for the acceptorless dehydrogenative coupling reactions to prepare quinoline derivatives, optimized conditions also facilitated the attainment of a series of quinoline derivatives with yields from 57 % to 95 %. During our exploration of the reactions, we also uncovered the presence of "metal-ligand" cooperation effect in the catalytic process.

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