C-H bond activation at cationic [(eta(5)-C5Me5)Ir(PMe2Ar')] centers is described, where PMe2Ar' are the terphenyl phosphine ligands PMe2Ar2Xyl and PMe2Ar2Dipp. Different pathways are defined for the conversion of the five-coordinate complexes [(eta(5)-(CMe5)-Me-5)-IrCl(PMe2Ar')1(+), 2(Xyl)(+) and 2(Dipp)(+), into the corresponding pseudoallyls 3(Xyl)(+) and 3(Dipp)(+). In the absence of an external Bronsted base, electrophilic, remote zeta C-H activation takes place, for which the participation of dicationic species, [(eta(5)-(CMe5)-Me-5)Ir-(PMe2Ar')](2+), is proposed. When NEt3 is present, the PMe2Ar2Dipp system is shown to proceed via 4(Dipp)(+) as an intermediate en route to the thermodynamic, isomeric product 3(Dipp)(+). This complex interconversion involves a non-innocent C5Me5 ligand, which participates in C-H and C C bond formation and cleavage. Remarkably, the conversion of 4(Dipp)(+) to 3(Dipp)(+) also proceeds in the solid state.