Implication of a σ-Methane Complex en Route to Elimination of Methane from a Ruthenium Complex: An Experimental and Theoretical Investigation

The five-coordinated 16-electron complex [Ru­(Me)­(dppe)₂]­[OTf] (<b>3</b>) undergoes methane elimination at room temperature to afford the ortho-metalated species [(dppe)­{(C₆H₅)­(C₆H₄)­PCH₂CH₂P­(C₆H₅)₂}­Ru]­[OTf] (<b>7</b>). Methane elimination, monitored using NMR spectroscopy, revealed no intermediate throughout the reaction. The NOE between Ru–Me protons and ortho phenyl protons and an agostic interaction trans to the methyl group were found in complex <b>3</b> by NMR spectroscopy, which form the basis for three plausible pathways for methane elimination and ortho metalation: pathway I (through spatial interaction), pathway II (through oxidative addition and reductive elimination), and pathway III (through agostic interaction). Methane elimination from complex <b>3</b> via pathway I was discounted, since it involves interactions through space and not through bonds. Moreover, the calculated energy barrier for the pathway I transition state was quite high (71.3 kcal/mol), which also indicates that this pathway is very unlikely. Furthermore, no spectroscopic evidence for oxidatively added seven-coordinated Ru­(IV) species was found and the computed energy barrier of the transition state for pathway II was moderately high (41.1 kcal/mol), which suggests that this cannot be the right pathway for methane elimination and ortho-metalation of complex <b>3</b>. On the other hand, indirect evidence in the form of chemical reactions point to the most plausible pathway for methane elimination, pathway III, via the intermediacy of a σ-CH₄ complex that could not be found spectroscopically. DFT calculations at several levels on this pathway showed an initial low-barrier rearrangement through <b>TS1</b> to a square-pyramidal intermediate wherein methyl and agostic C–H are cis to each other. Migration of hydrogen from agostic C–H and elimination of methane proceed through the transition state <b>TS2</b>, which retains a weak metal–H bonding through most parts of the reaction coordinate. Upon comparison of all three pathways, pathway III was found to be the most likely for methane elimination and ortho-metalation of complex <b>3