新型低价硼硅锗化合物的合成与表征

It is one of the most important branch of the theoretical chemistry to synthesize compounds of main group elements in low valence, including compounds of monovalent triels and divalent crystallogens, the research of which is quite limited in China currently. This project focuses on two of the most advanced directions in this area. i) Synthesis of new β-diketiminato boron(I) monomer, which is still unknown for many years after the report of β-diketiminato aluminum(I) and can be realized by synthesizing new β-diketiminato ligands with stable skeleton and adjustable side-groups. ii) Synthesis of aromatic heavier analogues of carbene chloride (metallylene chloride) with new ligands, which is a significant achievement for the area of low-valent main group elements to synthesize derivates of metallylenes and to develop coordination chemistry of metallylenes. In this project, monovalent boron and metallylenes will be stabilized in a suitable aromatic environment to obtain the target products mentioned above through new ligands and the stabilization effect of thermodynamics and kinetics. The project will exhibit high significance for the improvements of inorganic synthesis and corresponding chemical subjects in both theory and practice.

低价主族元素的分子合成化学，包括硼族元素一价化合物及碳族元素二价化合物的合成，具有重要的化学理论意义。目前该领域在国内无机化学界才刚刚起步。本项目对准该领域最前沿的两个热点问题立项。其一是合成新型β-二亚胺硼(I)的单体分子，该分子在β-二亚胺铝(I)出现多年后仍然是无机合成的空缺。新型β-二亚胺配体具有稳定的骨架和可调节大小的侧链基团，从而提高目标产物的合成可行性。其二是使用新配体来合成芳香性氯代重卡宾，这是低价主族元素合成领域具有里程碑意义的成果，为进一步合成各类重卡宾衍生物、发展重卡宾金属配位化学提供可能。本项目巧妙地设计了有机配体来稳定目标分子，同时合理地利用了热力学和动力学稳定化作用，使产品一价硼或重卡宾处于一个稳定的芳香环体系中，以实现目标分子的合成。项目对迅速提高国内无机合成的水平，发展中国化学学科有重大的理论和现实意义。

本项目以“新型低价硼硅锗化合物的合成”为研究目标，按照申请书计划推进课题研究。项目在主族元素的分子合成上，共取得以下8项成果：1）硼卡宾的异构和硼氧双键的合成；2）新型β-二亚胺的设计与合成；3）新型锗卡宾与锡卡宾的合成；4）新型β-二亚胺锗自由基的合成；5）钴诱导自由基锗卡宾异构生成双锗卡宾；6）新型β–二亚胺双锗宾的合成；7）新型β–二亚胺铝(I)的异构化反应；8）大体积α-二亚胺溴硼烷的合成。这其中两项成果已经发表，一向成果处于审稿阶段，另外的四项成果积累，将于近期撰文发表。.项目在执行过程中，根据出现的阶段性成果，进一步拓展了课题研究。.受项目支持，项目负责人建立了严格规范的无水无氧合成实验室，在主族元素无机合成的前沿领域实现了一系列成果积累，表现出良好的学术创新能力。