Novel Bonding Environments and Reactivity for Heavy Main Group Metals

该提案的主要目标是开发主族有机金属配合物（即铟和铋的那些）的丰富且可调的反应化学，并开发它们作为昂贵且有毒的过渡金属和稀土配位配合物的替代物用于绿色化学过程。 这是通过合成和表征新的刘易斯酸性和氧化还原活性化合物来实现的，这些化合物采用知情的配体设计来提供反应性金属中心。 将筛选所得化合物作为在各种水性和非水性反应条件下选择化学反应的催化剂的稳定性和反应性。 这项工作将在以下方面产生重大影响：1）合成有机、无机和有机金属化学--开发新的多官能硫醇配体和主族金属硫醇盐化合物的简便路线，以及鉴定In（II）/Bi（II）物种的新反应性以产生新的化学图案;和2）催化/绿色化学-通过筛选水解稳定的阳离子二硫醇铟和二硫醇铋作为用于生产生物燃料的水性介质中的反应的催化剂，以及筛选用于制备可生物降解和生物可再生聚合物的环酯的ROP的有机铟和铋双硫醇盐化合物。这些贡献将证明这些有机金属主族化合物作为可持续和环境友好技术开发的关键组成部分的潜力。

The primary goal of this proposal is to develop the rich and tunable reaction chemistry of main group organometallic complexes (i.e. those of indium and bismuth), and exploit their use as alternatives to expensive and toxic transition metal and rare earth coordination complexes for green chemical processes. This is being achieved through the synthesis and characterization of novel Lewis acidic and redox active compounds which employ informed ligand design to afford reactive metal centres. The resulting compounds will be screened for stability and reactivity as catalysts for select chemical reactions under various aqueous and non-aqueous reaction conditions. This work will have a high impact on: 1) synthetic organic, inorganic and organometallic chemistry - in the development of facile routes to new polyfunctional thiol ligands and main group metal thiolate compounds, and identification of new reactivity for In(II)/Bi(II) species to yield novel chemical motifs; and 2) catalysis/green chemistry - through the screening of hydrolytically stable cation indium- and bismuth bis-thiolates as catalysts for reactions in aqueous media for the production of biofuels, and the screening of organoindium and -bismuth bis-thiolate compounds for the ROP of cyclic esters for the preparation of biodegradable and biorenewable polymers. These contributions will demonstrate the hitherto under explored potential of these organometallic main group compounds as key components in the development of sustainable and environmentally friendly technologies.