Cp₂TiX Complexes for Sustainable Catalysis in Single‐Electron Steps

Abstract

In one word,h ow would you describe your research? Evolving, exciting, rewarding, dynamic! What is the most significant result of this study?Catalysis in single-electron steps merges the advantages of radical chemistry,s uch as high functional group tolerance, mild reaction conditions, and high rates, with those of transition-metal catalysis, such as control of stereoselectivity by the ligands of the metals. The key aspect of our approach is to perform oxidative additions and reductive eliminations in one-electron steps. Therefore, we make use of the same terms as in classical catalysis but significantly broaden the scope of old concepts. How is this approach related to other fields of catalysis?In many cross-coupling reactions and Lewis acid catalyzed processes the variation of the anionic ligands lead to an increase in reactivity and selectivity.F or catalysis in single-electron steps this is also the case. However,w ith cyclic voltammetry,w eh ave an ideal method that allows us to rationally screen the properties essential for reactivity.T his is not always straightforward in other branches of catalysis. Therefore, our approach is both related and unique.How did the collaborationo nt his project start?The collaboration started when Professors Gansäuer and Flowers met at an organic free radical conference in Ottawa in 2009. Since then they have tackled many mechanistic problems often with the aid of theoretical chemistry.

Mechanistic Study and Development of Catalytic Reactions of Sm(II)

“…During the last several years, we have studied a number of reported catalytic systems and learned a great deal that is useful in enabling the development of a robust and user-friendly approach to catalytic reactions of Sm(II). 48,49 We will focus on the approaches developed by Endo and Greeves, 40,41 but note that all of the systems we have examined to date have similar challenges. An example of a typical approach is shown in Scheme 1.…”