A family of dinuclear (salicylaldimato)zinc(mu(2)-alkoxide) complexes show unusual behavior, decomposing to olefins and the corresponding mu(2)-hydroxide complexes under very mild conditions in the solid state. The reaction in homogeneous solution is, on the other hand, not observable, even at elevated temperatures over extended periods of time. The reaction in the solid state occurs preferentially on one crystallographic face and displays kinetics characteristic of polymorphic transformations in single crystals.