Reactions of atomic cations with methane: gas phase room-temperature kinetics and periodicities in reactivity.

Reactions of methane have been measured with 59 atomic metal cations at room temperature in helium bath gas at 0.35 Torr using an inductively-coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer. The atomic cations were produced at approximately 5500 K in an ICP source and allowed to decay radiatively and to thermalize by collisions with argon and helium atoms prior to reaction. Rate coefficients and product distributions are reported for the reactions of fourth-row atomic cations from K(+) to Se(+), of fifth-row atomic cations from Rb(+) to Te(+) (excluding Tc(+)), of sixth-row atomic cations from Cs(+) to Bi(+), and of the lanthanide cations from La(+) to Lu(+) (excluding Pm(+)). Two primary reaction channels were observed: C-H bond insertion with elimination of H(2), and CH(4) addition. The bimolecular H(2) elimination was observed in the reactions of CH(4) with As(+), Nb(+), and some sixth-row metal cations, i.e., Ta(+), W(+), Os(+), Ir(+), Pt(+); secondary and higher-order H(2) elimination was observed exclusively for Ta(+), W(+), and Ir(+) ions. All other transition-metal cations except Mn(+) and Re(+) were observed to react with CH(4) exclusively by addition, and up to two methane molecules were observed to add sequentially to most transition-metal ions. CH(4) addition was also observed for Ge(+), Se(+), La(+), Ce(+), and Gd(+) ions, while the other main-group and lanthanide cations did not react measurably with methane.