Novel Bonding Environments and Reactivity for Heavy Main Group Metals

这一建议的主要目标是发展主族有机金属络合物(即铟和铋的络合物)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络合物的绿色化学过程的替代品。这是通过合成和表征新的Lewis酸性和氧化还原活性化合物来实现的，这些化合物使用知情的配体设计来提供活性金属中心。将筛选得到的化合物作为催化剂在各种水和非水反应条件下进行选择性化学反应的稳定性和反应活性。这项工作将对以下方面产生重大影响：1)合成有机、无机和有机金属化学-开发合成新的多官能硫醇配体和主族金属硫酸盐的简便途径，并鉴定In(II)/Bi(II)物种产生新的化学基序的新的反应性；以及2)催化/绿色化学-通过筛选可水解性稳定的阳离子铟和铋双硫酸盐作为催化剂在水介质中反应生产生物燃料，以及筛选用于环酯反应的有机铟和铋双硫化合物以制备可生物降解和可生物缠绕的聚合物。这些贡献将展示这些有机金属主族化合物作为开发可持续和环境友好型技术的关键组成部分的迄今尚未开发的潜力。

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.