Abstract: Disclosed is a polyol/polyisocyanate adhesive system having an isocyanate component and a catalyzed component which form a heat-cured composition when admixed and heated above a threshold temperature. The catalyzed component has a hydroxyl-functional component catalyzed with a catalyst combination of a heat-activatable amine or amine-like catalyst which is activated at temperatures above the threshold temperature, and an activatable complexed metal catalyst comprising the reaction product of tin or bismuth catalysts, or a mixture thereof, and a molar excess of a mercapto compound complexing agent. The catalyst combination is effective to maintain the processibility of the system at ambient temperatures while promoting the rapid cure of the system when heated above the threshold temperature.