Generation of ditetrelynes by B-O bond elimation: bond activation and catalysis

通过 B-O 键消除生成二四烯：键活化和催化

• 批准号: 2599281
• 金额: --
• 依托单位: University of Bath
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2021
• 资助国家: 英国
• 起止时间: 2021 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2599281
• 关键词: Generation; ditetrelynes; bond; elimation; activation

This project will investigate the formation of low-valent group 14 compounds under catalyticaly relevant conditions via the formation of strong E'-O bonds (E' = B, Al, Si). These ditetrelynes will then be investigated for their reductive bond activation capacity towards a range of organic and inorganic substrates and subsequently applied in catalytic transformations.Stage 1:The project will initially focus on the formation of a range of terphenyl supported divalent group 14 alkoxides which will act as precatalysts. With these species in hand their reactivity towards E'-E' species will be targeted to generate species of the form LEEL (E = Ge, Sn; L = terphenyl) which contain E(I) centres.Stage 2:The reactivity of LEEL species (E = Ge, Sn; L = terphenyl) towards organic substrates containing reducible fragments such as heterocumulenes, alkenes, carbonyl derivatives; small molecules such as H2, CO, ethene and inorganic molecules such as phosphine oxides, tetravalent tetrels and isosteric, isoelectronic alkene analogues such as ammonia borane derivates will be investigated.Stage 3:With validated reductive steps and new methodologies to reform LEEL species under catalytically relevant conditions in hand, we will investigate the catalytic borylative reduction of the aforementioned substrates. Mechanistic insight will be sought via standard physical inorganic techniques, as well as operando spectroscopy.This work will seek to validate the efficacy of low valent main group fragments in redox cycling for catalysis. Such a mechanistic approach would be unique and is one of the "holy grails" of main group chemistry today. The implications for the uptake of Earth abundant and green catalysis would be profound by replacing precious metal catalysis. This will contribute to Britain's world leading position in fine chemicals. This work fits within the EPSRC's ongoing interest in catalysis.Dr Ruth Webster will act as second supervisor as a result of her extensive experience in the area of Earth abundant metal catalysis and she will provide input on mechanistic insight, new reaction development and in situ analysis of reactivity.

本项目将研究在催化相关条件下通过形成强E '-O键（E' = B，Al，Si）形成低价14族化合物。这些ditetrelynes然后将被调查的还原键活化能力对一系列的有机和无机substrates和随后在催化transformation.Stage 1的应用：该项目将首先集中在形成一系列的三联苯支持的二价14族醇盐将作为预催化剂。有了这些物质，它们对E '-E'物质的反应性将被靶向以产生LEEL形式的物质（E = Ge，Sn; L =三联苯）。第二阶段：LEEL物种的反应性（E = Ge，Sn; L =三联苯）对含有可还原片段的有机底物，例如杂累积多烯、烯烃、羰基衍生物;将研究小分子如H2、CO、乙烯和无机分子如氧化膦、四价四元化合物和等排、等电子烯烃类似物如氨硼烷衍生物。随着有效的还原步骤和新的方法学在催化相关条件下改革LEEL物种，我们将研究上述底物的催化硼化还原。通过标准的物理无机技术以及操作光谱学来寻求机理上的见解。这项工作将寻求验证低价主基片段在氧化还原循环催化中的功效。这种机械方法是独一无二的，是当今主族化学的“圣杯”之一。通过取代贵金属催化剂，对地球丰富和绿色催化剂的吸收将产生深远的影响。这将有助于英国在精细化学品领域的世界领先地位。这项工作符合EPSRC对催化的持续兴趣。Ruth韦伯斯特博士将担任第二主管，因为她在地球丰富的金属催化领域拥有丰富的经验，她将提供关于机理洞察，新反应开发和反应活性原位分析的投入。