From Nuclear Fuels to CO2 Activation at Uranium Complexes - Chemistry Between Phobia & Enthusiasm

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• Prof. Dr Karsten Meyer, Friedrich-Alexander-University Erlangen-Nuremberg
• Thursday 24 November 2011, 14:00-15:00
• Unilever Lecture Theatre, Department of Chemistry.

If you have a question about this talk, please contact Sian Bunnage.

Uranium and, its in traces existing heavier neighbor, plutonium, are the heaviest naturally occurring elements, and they share one common thing with each other: they undeniably have the worst reputation of all elements of the periodic table. Negative connotations through news on warlords and nuclear reactor catastrophes fuel the fear to handle and manipulate the element uranium; even within the scientific community. However, human life on earth would not exist, and the exploration of the far universe would not be possible without natural radioactivity. In this lecture, a general introduction is given on how radioactivity of naturally abundant and man-made elements, in e.g. plutonium-powered heart pacemakers and satellites, impact our modern life. A brief tour through basic inorganic chemistry shows how pitchblende is transformed into modern nuclear fuels, how organometallic chemists have discovered the element for basic chemical research, and how this field has sparked new discoveries of current interest ever since. In our efforts to activate small molecules of industrial and biological relevance, we have turned our attention to coordinative unsaturated, highly reactive, low- and high-valent uranium coordination complexes. For instance, the Werner-type hexadentate tris(aryloxide) tri¬aza¬cyclo¬nonane chelating ligand, (t-BuArO)3tacn3–, and its sterically more demanding and protective adamantyl derivative have provided access to reactive coordination compounds of uranium, [((RArO)3tacn)U] (R = t-Bu, Np, Ad), in oxidation states III , IV, V, and VI and custom-tailored ligand environments. These complexes display a pronounced reactivity towards carbon dioxide and related small molecules.

Here, reactions are presented that result in CO2 coordination, activation, “disproportionation”, splitting, insertion, and functionalization. It is shown that charge-separated complexes of uranium are particularly reactive species that often lead to unprecedented chemistry.

Leading References: [1] S.J. Zuend, O.P.Lam, F.W. Heinemann and K. Meyer
in Angew. Chem. Int. Ed. 2011, 50, in press. VIP paper [2] O.P. Lam, F.W. Heinemann and K. Meyer in
Angew. Chem. Int. Ed. 2011, 50, 5965. [3] O.P. Lam, S.C. Bart, F.W. Heinemann and K. Meyer in Chem. Comm. 2010,46, 3137. [4] A.R. Fox, S.C. Bart, C. Anthon, K. Meyer and C.C. Cummins in Nature 2009, 455, 341. [5] S.C. Bart, C. Anthon, F.W. Heinemann, E. Bill, N.M. Edelstein and K. Meyer in J. Am. Chem. Soc. 2008, 130, 12536. [6] I. Castro-Rodriguez and K. Meyer in J. Am. Chem. Soc. 2005, 127, 11242. [7] I. Castro-Rodriguez, H. Nakai, L. Zakharov, A.L. Rheingold and K. Meyer in Science 2004, 305, 1757.

This talk is part of the Materials Chemistry Research Interest Group series.

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