Augmentation of Alkaline Earth Reactivity: An FLP Analogy

碱土反应性的增强：FLP 类比

• 批准号: EP/N014456/1
• 负责人: Michael Hill
• 金额: $ 94.17万
• 依托单位: University of Bath
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2016
• 资助国家: 英国
• 起止时间: 2016 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FN014456%2F1
• 关键词: Augmentation; Alkaline; Earth; Reactivity; FLP

Catalysis, the acceleration of chemical transformation, is the key to realising environmentally friendly and economical processes for the conversion of both conventional (fossil) and alternative (e.g. biomass and carbon dioxide) chemical feedstocks. Catalysts act by reducing the energy required for a reaction to proceed and will, thus, occupy a key role in the world's energy future. Many of the most useful soluble and solid catalysts incorporate precious metals such as rhodium, palladium, platinum and ruthenium. These metals are expensive and their supply is limited. There is, therefore, a need for the development of non-precious-metal catalysts as replacements.In response to these requirements, the last decade has seen emergence of s- and p-block compounds as inexpensive and ecologically benign catalytic reagents. The applicant's previous research has led the way in the development of group 2 reagents, particularly those based on magnesium and calcium (the eight and four most earth-abundant elements respectively) for a wide variety of catalytic transformations. Although this has included some of the most practically desirable transformations, the usefulness of currently available group 2 reagents is limited by their absolute reactivity. A detailed mechanistic approach to the study of these reactions has allowed the emergence of more generalised models for the chemical reactivity of these previously under-appreciated elements. This understanding is based on a polarisation model intrinsic to the bonding of most substrate molecules to a highly electropositive group 2 centre. The charge separation induced across a substrate molecule by these species may be viewed as resulting from reactivity closely related to another emerging field, 'frustrated' Lewis pair chemistry. In this latter case, a wide variety of small molecules may be activated through a cooperative interaction of a high energy vacant molecular orbital and a low energy filled atomic orbital. This proposal wishes to extrapolate this hydpothesis to apply the FLP concept to design new group 2 species of unparalleled reactivity. In so doing the new reagents will enable catalytic systems that combine the environmental and fiscal benefits of group 2 chemistry with the enhanced and readily manipulated FLP reactivity.

催化是化学转化的加速过程，是实现传统（化石）和替代（例如生物质和二氧化碳）化学原料转化的环境友好和经济过程的关键。催化剂的作用是减少反应进行所需的能量，因此将在世界能源的未来中发挥关键作用。许多最有用的可溶性和固体催化剂包含贵金属，例如铑、钯、铂和钌。这些金属价格昂贵，供应有限。因此，有必要开发非贵金属催化剂作为替代品。为了响应这些需求，在过去的十年中出现了s-和p-嵌段化合物作为廉价和生态友好的催化剂。申请人之前的研究已经在第2组试剂的开发中处于领先地位，特别是基于镁和钙（分别是地球上最丰富的八种和四种元素）的试剂，用于各种催化转化。虽然这包括了一些最实际需要的转化，但目前可用的第2组试剂的有用性受到其绝对反应性的限制。一个详细的机制的方法来研究这些反应已经允许出现更普遍的模型，这些以前被低估的元素的化学反应性。这种理解是基于大多数底物分子与高正电性2族中心结合所固有的极化模型。由这些物质在底物分子上诱导的电荷分离可以被视为与另一个新兴领域“受抑”刘易斯对化学密切相关的反应性的结果。在后一种情况下，各种各样的小分子可以通过高能空分子轨道和低能填充原子轨道的协同相互作用而被活化。该提案希望将此假设外推到应用FLP概念来设计具有无与伦比的反应性的新的第2组物种。这样做，新试剂将使催化体系能够将第2类化学的环境和财政效益与增强的和容易操纵的FLP反应性结合联合收割机。

项目成果

Alkaline-Earth Derivatives of Diphenylphosphine-Borane

二苯基膦硼烷的碱土衍生物

• DOI: 10.1021/acs.organomet.0c00008
• 发表时间: 2020
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Morris L

Phosphinoborane interception at magnesium by borane-assisted phosphine-borane dehydrogenation.

通过硼烷辅助的膦-硼烷脱氢作用对镁进行膦硼烷拦截。

• DOI: 10.1039/d0dt03415k
• 发表时间: 2020
• 期刊: 2003)
• 作者: Morris LJ

A computational study on the identity of the active catalyst structure for Ru(ii) carboxylate assisted C-H activation in acetonitrile.

乙腈中 Ru(ii) 羧酸盐辅助 C-H 活化活性催化剂结构鉴定的计算研究。

• DOI: 10.1039/c9ob01092k
• 发表时间: 2019
• 期刊: Organic & biomolecular chemistry
• 影响因子: 3.2
• 作者: McMullin CL

Multimetallic Alkaline-Earth Hydride Cations

• DOI: 10.1021/acs.organomet.9b00493
• 发表时间: 2019-10-14
• 期刊: ORGANOMETALLICS
• 影响因子: 2.8
• 作者: Garcia, Lucia;Mahon, Mary F.;Hill, Michael S.
• 通讯作者: Hill, Michael S.