Evidence for C-F Bond Formation through Formal Reductive Elimination from Tellurium(VI)

The fundamental challenge of C-F bond formation by reductive elimination has been met by compounds of select transition metals and fewer main group elements. The work detailed herein expands the list of main group elements known to be capable of reductively eliminating a C-F bond to include tellurium. Surprising and novel modes of both sp(2) and sp(3) C-F bond formation were observed alongside formation of Te-IV cations during two separate attempts to synthesize/characterize fluorinated organotellurium(VI) cations in superacidic media (SbF5/SO2ClF). Following detailed low-temperature NMR experiments, the mechanisms of the two unique reductive elimination reactions were probed and investigated using density functional theory (DFT) calculations. Ultimately, we found that an indirect reductive elimination pathway is likely operative whereby Sb plays a key role in fluoride abstraction and C-F bond formation, as opposed to unimolecular reductive elimination from a discrete Te-VI cation.

Automated summary

This study demonstrates the ability of main group elements such as tellurium to undergo reductive elimination of C-F bonds in superacidic media, revealing different modes of C-F bond formation and the generation of Te-IV cations. Utilizing DFT calculations, the mechanisms of the two unique reductive elimination reactions were investigated.