Well-Defined Cationic Bismuth Compounds: Fundamental Properties and Applications in Synthesis and Catalysis

基于重主族元素的分子化合物具有固有的高官能团耐受性和软刘易斯酸，以及相对较高的（中间）自由基的稳定性。这些特征，结合现代合成化学方法，使得这些化合物在合成和催化方面的应用具有吸引力，可以作为基于s-嵌段或过渡金属的方法的补充。本研究项目主要研究铋的分子化合物，铋是一种低毒性的非贵重元素，与Li、Mg、Al、Sn等主族元素相比，其基础化学和应用化学尚不发达。对非常规铋化合物进行详细的设计、合成和分析，以开发新的合成和催化试剂。目标铋化合物是(i)具有简单单齿配体的阳离子物质和（ii）具有氧化还原活性配体的中性和阳离子配合物。这些化合物有望出现新的反应模式，其中一些已经在初步工作中被发现。这些将被合理化、扩展并转化为合成方法和催化应用。在CH活化、配体稳定的铋自由基和选择性CO2还原等领域有望取得重大进展。

Molecular compounds based on heavy main group elements show an intrinsically high functional group tolerance along with a soft Lewis-acidity, and a relatively high stability of (intermediate) radical species. These characteristics, combined with modern approaches in synthetic chemistry make such compounds attractive for applications in synthesis and catalysis that can be complementary to approaches based on s-block or transition metals. This research project is focused on molecular compounds of bismuth, a non-precious element of low toxicity, the fundamental and applied chemistry of which is underdeveloped compared to that of other main group elements such as Li, Mg, Al, or Sn. Non-conventional bismuth compounds will be designed, synthesized and analyzed in detail towards the development of new reagents for synthesis and catalysis. The targeted bismuth compounds are (i) cationic species with simple monodentate ligands and (ii) neutral and cationic complexes with redox-active ligands. New reactivity patterns are expected for these compounds, some of which have already been uncovered in preliminary work. These will be rationalized, extended, and turned into synthetic methods and catalytic applications. Significant advances are expected in the fields of CH activation, ligand-stabilized bismuth radicals, and selective CO2 reduction.