Mechanism and Energetics for Dehydrogenation of Methane by Gaseous Iridium Ions
Jason K. Perry, Gilles Ohanessian, William A. Goddard III
Abstract
Ir^+ has been observed as the most efficient transition-metal ion for dehydrogenation of CH_4 in the gas phase. We carried out theoretical studies of the complete reaction profile for this process and find three salient factors responsible for the high reactivity: (i) the ability of Ir^+ to change spin easily, (ii) the strength of the Ir-C and Ir-H bonds, and (iii) the ability of Ir^+ to form up to four covalent bonds. We show that among transition-metal ions Ir^+ is unique in best possessing all three characteristics. The combination of these factors leads to a global minimum for the singlet Ir(H)_2(CH_2)^+ structure, which plays an important role in the activation. On the basis of these results, we suggest solution-phase analogues that may also activate CH_4.
Group Members
Perry, J. K., Ohanessian, G., & III, W. A. G. (1994). Mechanism and Energetics for Dehydrogenation of Methane by Gaseous Iridium Ions. *Organometallics*, *13*(5), 1870-1877. https://doi.org/10.1021/om00017a050