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Details of Grant 

EPSRC Reference: EP/I031545/1
Title: Bond Activation - the Remarkable Emerging Chemistry of Bis(carboranes)
Principal Investigator: Welch, Professor AJ
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department: Sch of Engineering and Physical Science
Organisation: Heriot-Watt University
Scheme: Standard Research
Starts: 01 September 2012 Ends: 28 February 2017 Value (£): 504,365
EPSRC Research Topic Classifications:
Chemical Synthetic Methodology
EPSRC Industrial Sector Classifications:
No relevance to Underpinning Sectors
Related Grants:
Panel History:
Panel DatePanel NameOutcome
08 Sep 2011 EPSRC Physical Sciences Chemistry - September 2011 Announced
Summary on Grant Application Form
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.
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Organisation Website: http://www.hw.ac.uk