A study related to isomerism brought about by the two different chelation modes of the residual double bond resulting from the intramolecular Pauson-Khand reaction in [(diallylamino) alkynylcarbene] tungsten complexes was undertaken. The presence of a stereogenic center on the carbene ligand in the cycloadduct caused a clear difference in energy between the two diastereomeric forms resulting from alkene chelation. The energy barrier involved in their interconversion was determined by means of dynamic HPLC (D-HPLC) experiments, and its relative high value was related to the difficulty of the inversion at the nitrogen center due to structural rigidity.