Novel Bonding Environments and Reactivity for Heavy Main Group Metals

本提案的主要目标是开发丰富和可调的主要族有机金属配合物（即铟和铋的配合物）的反应化学，并利用它们作为绿色化学过程中昂贵和有毒的过渡金属和稀土配合物的替代品。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活性金属中心。所得到的化合物将在各种水和非水反应条件下作为选定化学反应的催化剂进行稳定性和反应性筛选。这项工作将对以下方面产生重大影响：1)有机、无机和有机金属化学合成——开发新的多官能团硫醇配体和主基团金属硫醇化合物的便捷途径，并鉴定新的in (II)/Bi（II）物质的反应性，从而产生新的化学基序；2)催化/绿色化学——通过筛选水解稳定的阳离子铟和铋双硫酸盐作为水介质反应的催化剂，用于生产生物燃料，以及筛选有机铟和铋双硫酸盐化合物作为环酯的ROP，用于制备生物可降解和生物可再生的聚合物。这些贡献将表明这些有机金属主族化合物作为发展可持续和环境友好型技术的关键组成部分的潜力迄今尚未得到充分开发。

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.