We report the transfer-dehydrogenation of gas-phase alkanes catalyzed by solid-phase, molecular, pincer-ligated iridium catalysts, using ethylene or propene as hydrogen acceptor. Iridium complexes of sterically unhindered pincer ligands such as (PCP)-P-iPr4, in the solid phase, are found to give extremely high rates and turnover numbers for n-alkane dehydrogenation, and yields of terminal dehydrogenation product (alpha-olefin) that are much higher than those previously reported for solution-phase experiments. These results are explained by mechanistic studies and DFT calculations which jointly lead to the conclusion that olefin isomerization, which limits yields of alpha-olefin from pincer-Ir catalyzed alkane dehydrogenation, proceeds via two mechanistically distinct pathways in the case of ((PCP)-P-iPr4)Ir. The more conventional pathway involves 2,1-insertion of the alpha-olefin into an Ir-H bond of ((PCP)-P-iPr4)IrH2, followed by 3,2-beta-H elimination. The use of ethylene as hydrogen acceptor, or high pressures of propene, precludes this pathway by rapid hydrogenation of these small olefins by the dihydride. The second isomerization pathway proceeds via alpha-olefin C-H addition to (pincer)Ir to give an allyl intermediate as was previously reported for ((PCP)-P-iPr4)Ir. The improved understanding of the factors controlling rates and selectivity has led to solution-phase systems that afford improved yields of alpha-olefin, and provides a framework required for the future development of more active and selective catalytic systems.