The dynamics of the product channels forming OCF++H++HF and HCF2++H++O following the collisions of CF22+ with H2O have been investigated with a new position-sensitive coincidence experiment at a center-of-mass collision energy of 5.6 eV. The results show the formation of OCF+ occurs via the formation of a doubly charged collision complex [H2O-CF2](2+) which subsequently undergoes a charge separating dissociation to form H+ and HOCF2+. The HOCF2+ monocation subsequently fragments to form HF+OCF+. The lifetimes of the collision complex and the HOCF2+ ion are at least of the order of their rotational period. The kinetic energy release in this reaction indicates that it involves the ground state of CF22+ and forms the ground electronic states of OCF+ and HF. The mechanism for forming HCF2+ involves the direct and rapid abstraction of a hydride ion from H2O by CF22+. The resulting OH+ ion subsequently fragments to H++O, on a time scale at least comparable with its rotational period. (C) 2004 American Institute of Physics.