Electrophiles such as Me+ Ag+, or protons react with the five-coordinate Ir(III) complex [IrClH(biPSi)] (biPSi = kappa-P,P, Si-Si(Me){(CH2)(3)PPh2}(2)) by abstracting its chloride ligand. The resulting species can be stabilized by a variety of L ligands to give the cationic complexes [IrH(biPSi)L-2](+). The derivative [IrH(biPSi)(NCMe)(2)](+) has been subjected to a kinetic study regarding the facile dissociations of its acetonitrile ligands. The presence of water changes the course of the reaction producing dihydride complexes that contain the silanol ligand kappa-O, P,P-HOSi(Me){(CH2)(3)PPh2}(2) (biPSiOH). The water activation product [IrH2(biPSiOH)(NCMe)](CF3SO3) undergoes insertion reactions with ethylene and phenylacetylene. The use of hydrolyzable fluorinated counterions such as PF6- or BF4- further modifies the reaction by provoking the incorporation of fluoride at the silicon atom of the former biPSi ligand. The dihydride resulting after such a process, [IrH2(biPSiF)(NCMe)]BF4 (biPSiF = kappa-P-2-FSi(Me){(CH2)(3)PPh2}(2)), displays a trans-chelating diphosphine ligand. When dehydrogenating the Ir center, spontaneously or using ethylene as hydrogen acceptor, the diphosphine backbone undergoes a Si-C bond cleavage leading to a new Ir(III) species with kappa-P,Si and kappa-C,P chelate ligands.