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.

该提案旨在理解并建立在申请人实验室最近发现的三个非凡反应的基础上。在第一个反应中，在金属硼烷（主要是]硼，碳和金属的簇化合物中，在室温下切割芳香族C-C键，该键是衍生自bis（Carborane）（Carborane）（两个连接的碳/硼簇）的。反应是显着的，因为竞技场中的C-C键非常强，通常被认为很难破裂。在第二个反应中，再次在室温下，另一种BIS（Carborane）分子似乎从其一半中丢失了两个碳顶点，因为它是一个完整的C2单位，并与金属碎片进行了降低和随后的反应。这种脱碳在异质化学中是前所未有的。最终反应（再次室温）证实了相关单碳纤维的Unabiguoulsy脱碳。同样，这是没有先例的。总而言之，第一个和第二个反应涉及双（carboranes），第三个反应是从具有非常强烈的电子吸引取代基的carborane开始。显然，这些前所未有的反应在某种程度上与这些卡伯纳人的非标准性质有关。不知何故，bis（carborane）和高度改良的卡堡正在促进传统上非常高的能量过程的粘结裂解反应。这两种类型的Carborane的化学成分目前都严重发达。该提案旨在通过对BIS（Carboranes）和Carboranes的反应进行详细研究，以解决这种情况，以电子绘制的取代基的反应，尤其集中在剥离或还原上，然后是金属化或人力化。我们完全期望这项研究将揭示除了最近发现的其他反应。通过一项全面的合成化学计划，我们将寻求识别和理解我们发现的非凡反应的起源。一旦我们理解它们，我们将处于更好的位置，以确定它们的一般性以及如何使用它们。