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Bond Activation - the Remarkable Emerging Chemistry of Bis(carboranes)

键活化——双（碳硼烷）的卓越新兴化学

基本信息

批准号：
EP/I031545/1
负责人：
Alan Welch
金额：
$ 64.27万
依托单位：
Heriot-Watt University
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2012
资助国家：
英国
起止时间：
2012 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FI031545%2F1
关键词：
Bond Activation Remarkable Emerging Chemistry

项目摘要

This proposal seeks to understand and build on three remarkable reactions recently discovered in the applicant's laboratory. In the first reaction an aromatic C-C bond is cleaved at room temperature in a metallacarborane (a cluster compound of [mainly] boron, carbon and metal) derived from a bis(carborane) (two linked carbon/boron clusters). The reaction is remarkable because C-C bonds in arenes are extremely strong and generally considered difficult to break. In the second reaction, again at room temperature, a different bis(carborane) molecule appears to lose two carbon vertices from one of its halves as an intact C2 unit on reduction and subsequent reaction with a metal fragment. Such decarbonation in this way is unprecedented in heteroborane chemistry. The final reaction (again room temperature) confirms unambiguoulsy decarbonation from a related monocarborane; again this is without precedent.In summary then, the first and second reactions involve bis(carboranes) and the third starts with a carborane with very strongly electron-withdrawing substituents. It seems apparent that these unprecedented reactions are in some way linked to the non-standard nature of these carboranes. Somehow the bis(carborane) and the highly modified carborane are promoting bond cleavage reactions that are traditionally very high energy processes. The chemistries of both these types of carborane are currently severely under-developed. The proposal seeks to address this situation by a thorough investigation of the reactions of bis(carboranes) and of carboranes with e-withdrawing substituents, focussing in particular on deboronation or reduction followed by metallation or capitation. We fully expect that this study will reveal other unexpected and novel reactions in addition to those recently found.Through a comprehensive synthetic chemistry programme we will seek to identify and understand the origins of the remarkable reactions we have discovered. Once we understand them we will be in a much better position to establish their generality and how they might be used.

该提案试图理解并建立在申请人实验室最近发现的三个显着反应的基础上。在第一个反应中，芳香族C-C键在室温下在衍生自双（碳硼烷）（两个连接的碳/硼簇）的金属碳硼烷（[主要]硼、碳和金属的簇化合物）中裂解。该反应是显着的，因为芳烃中的C-C键非常强，通常被认为很难断裂。在第二个反应中，同样在室温下，不同的双（碳硼烷）分子似乎在还原和随后与金属片段反应时从其一半中的一个失去两个碳顶点作为完整的C2单元。这种方式的脱碳在杂硼烷化学中是前所未有的。最后的反应（同样是室温）证实了从相关的单碳硼烷的明确的脱碳酸作用;同样这是没有先例的。总之，第一和第二反应涉及双（碳硼烷），第三反应从具有非常强的吸电子取代基的碳硼烷开始。很明显，这些前所未有的反应在某种程度上与这些碳硼烷的非标准性质有关。不知何故，双（碳硼烷）和高度改性的碳硼烷正在促进传统上非常高能量的过程的键断裂反应。这两种类型的碳硼烷的化学性质目前严重开发不足。该提案试图通过彻底研究双（碳硼烷）和碳硼烷与吸电子取代基的反应来解决这种情况，特别关注脱硼或还原，然后进行金属化或头化。我们完全期望这项研究将揭示除了最近发现的那些之外的其他意想不到的和新颖的反应。通过一个全面的合成化学计划，我们将寻求识别和理解我们发现的显着反应的起源。一旦我们理解了它们，我们就能更好地确定它们的普遍性以及如何使用它们。