A Convergent Synthesis Approach to Uranium-Carbon Triple Bonds for Alkyne Metathesis Reactions.

• Applicant: Professor Dr. Karsten Meyer
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2008 to 2011
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 49373872

In transition-metal chemistry, alkylidyne complexes are of interest for the role that they play in alkyne metathesis catalysis. The best-known catalysts for the alkyne metathesis reaction have the formula RC≡M(OR)3 with M = Mo, W, are commercially available compounds, and were originally discovered by R. Schrock. The Cummins group is experienced with and has made contributions to alkyne metathesis. It was shown that complexes of the formula R1C≡Mo(N[i-Pr]Ar)3 are “universal” catalyst precursors, because their treatment with 3 R2OH produces active alkyne metathesis catalysts of formula R1C≡Mo(OR2)3. A major component of the Meyer research program is the activation of small molecules at reactive uranium complexes. These complexes have a sterically protected single binding site available for reaction chemistry. A highlight of this work has been the binding and activation of carbon dioxide through a single oxygenuranium interaction (η1-O-CO2). For the research proposed herein, the principle of “convergent synthesis” is embodied by our combination of the tacn-triphenolate uranium platform with Cummins’ early transition-metal reagents. The aim of this convergent effort is to uncover the first uranium alkylidyne (U≡CR) complexes and to probe their activity in alkyne metathesis.

• DFG Programme: Research Grants
• International Connection: USA
• Participating Person: Professor Christopher C. Cummins