The selective functionalization of alkanes and alkyl groups is a major goal of chemical catalysis. Toward this end, a bulky triphosphine with a central secondary phosphino group, bis(2-di-t-butyl-phosphinophenyl)phosphine (tBuPHPP), has been synthesized. When complexed to iridium, it adopts a meridional ("pincer") configuration. The secondary phosphino H atom can undergo migration to iridium to give an anionic phosphido-based-pincer (tBuPPP) complex. Stoichiometric reactions of the (tBuPPP)Ir complexes reflect a distribution of steric bulk around the iridium center in which the coordination site trans to the phosphido group is quite crowded; one coordination site cis to the phosphido is even more crowded; and the remaining site is particularly open. The (tBuPPP)Ir precursors are the most active catalysts reported to date for dehydrogenation of n-alkanes, by about 2 orders of magnitude. The electronic properties of the iridium center are similar to that of well-known analogous (RPCP)Ir catalysts. Accordingly, DFT calculations predict that (tBuPPP)Ir and (tBuPCP)Ir are, intrinsically, comparably active for alkane dehydrogenation. While dehydrogenation by (RPCP)Ir proceeds through an intermediate trans-(PCP)IrH2(alkene), (tBuPPP)Ir follows a pathway proceeding via cis-(PPP)IrH2(alkene), thereby circumventing unfavorable placement of the alkene at the bulky site trans to phosphorus. (tBuPPP)Ir and (tBuPCP)Ir, however, have analogous resting states: square planar (pincer)Ir(alkene). Alkene coordination at the crowded trans site is therefore unavoidable in the resting states. Thus, the resting state of the (tBuPPP)Ir catalyst is destabilized by the architecture of the ligand, and this is largely responsible for its unusually high catalytic activity.