Reactions of FeCH2(+) and CoCH2(+) with Aliphatic Alkanes in the Gas Phase. Activation of C-H and C-C Bonds by Naked Transition-Metal Carbene Ions

Article abstract of DOI:10.1021/ja00301a001

Gas-phase reactions of the title carbenes with several aliphatic alkanes using Fourier transform mass spectrometry (FTMS) ,are described.CoCH2(+) reacts with alkanes larger than methane whereas FeCH2(+) reacts with alkanes larger than ethane.Both FeCH2(+) and CoCH2(+) react predominantly by initial C-H bond insertion with some C-C bond insertion also observed.As a consequence of facile carbene-alkyl coupling, C-C bond cleavage processes proceed predominantly with elimination of the original carbene incorporated into the departing alkane neutral.In addition a small amount of C-C bond formation product is also observed.Finally, a greater degree of H/D scrambling is observed for CoCD2(+) than for FeCD2(+).