The reactions of O22+ with CH4, C2H2 and C2H4 have been investigated for the first time, using a position-sensitive coincidence technique, at centre-of–mass collision energies close to 4 eV. The experiments show these interactions yield a wide variety of products which involve the formation of new chemical bonds. The mechanisms of these bond-forming reactions have been investigated be examining the correlations between the velocities of the reactant and product ions which are revealed by the coincidence data. Many of the bond-forming reactions occur via the stripping of an atom (or group of atoms) from the neutral by the O22+ reactant, whilst other reactions clearly involve the initial formation of a collision complex which then fragments to form the detected products.