Details of Grant 

EPSRC Reference:	EP/M023885/1
Title:	Activation and Functionalisation of Carbon Dioxide by Low Valent Uranium Complexes
Principal Investigator:	Cloke, Professor G
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department:	Sch of Life Sciences
Organisation:	University of Sussex
Scheme:	Standard Research
Starts:	01 May 2015	Ends:	30 April 2018	Value (£):	320,303
EPSRC Research Topic Classifications:	Catalysis & Applied Catalysis Co-ordination Chemistry Electrochemical Science & Eng. Physical Organic Chemistry
EPSRC Industrial Sector Classifications:	No relevance to Underpinning Sectors
Related Grants:
Panel History:	Panel Date Panel Name Outcome 12 Feb 2015 EPSRC Physical Sciences Chemistry - February 2015 Announced
Summary on Grant Application Form
The use of well-defined molecular compounds to activate environmentally and industrially important small molecules has spearheaded advances in chemical transformations in an energy and atom efficient manner, and has expanded the scope of using such small, abundant molecules to produce commodity and high-added value chemicals. The emergence of CO2 as a climate-changing small molecule, coupled with the depletion of fossil fuels as feedstocks for the petrochemical industry and energy production, has led to significant amount of research into the use of CO2 as a potential precursor to more complex organic compounds. In recent years, the use of organometallic uranium complexes for small molecule activation, an area pioneered by the PI and others, has attracted significant interest and advances towards uranium-based catalysis have elevated these academically interesting molecules to a very active area of research worldwide. We have recently reported (Chemical Science, 2014, 3777-3788) a class of uranium(III) complexes which, for the first time, can be tuned to selectively activate CO2 in three different ways: reduce to CO and a uranium-oxo complex, reductively disproportionate to CO and a uranium-carbonate complex, or reductively couple to a uranium oxalate complex. The latter is particularly significant in that it involves C-C bond formation from CO2, a reaction previously rarely achieved with well-defined complexes. The control of selectivity and the establishment of the different mechanisms and key intermediates for these reductive activations means that we are can now think about how to use these uranium compounds to combine CO2 with a second, different small molecule. - thus generating new, useful organic compounds directly from CO2. In this project we will use both our existing and new uranium(III) complexes to target the coupling of CO2 to small molecules such as dihydrogen, alkenes and alkynes in order to build simple organic fragments such as formate, methoxide or dicarboxylates on the uranium centre. We will explore the mechanisms of these reactions, both experimentally and (in collaboration) computationally, and investigate both chemical and electrochemical routes for release of the CO2 -derived organic products from the uranium centres. Whilst this work may not lead directly to a catalytic process for converting CO2 into valuable organic chemicals or fuels, a fundamental understanding of the ways in which molecular inorganic compounds can bind, activate and functionalise CO2 is one of the keys to making such a process a reality.
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Organisation Website:	http://www.sussex.ac.uk