Control of HC(sp 3 ) Bond Cleavage Stoichiometry: Clean Reversible Alkyl Ligand Exchange with Alkane in [LPt(Alk)(H) 2 ] + (L=[2.1.1]‐(2,6)‐Pyridinophane)

Reversible alkane oxidative addition occurs to transient [LPtH]+ (L=[2.1.1]-(2,6)-pyridinophane; see scheme), which is generated at 86 °C from [LPtMe(H)2]+ in 1:1 hydrocarbon/CD2Cl2 mixtures. DFT calculations reveal why [LPtMe(H)2]+ eliminates methane, not dihydrogen, and why, in contrast to [LPtMe2H]+, no alkane dehydrogenation occurs.