Quantitative energy-resolved collision-induced dissociation cross-sections by tandem ESI-MS provide absolute thermochemical data for phosphine binding energies in first- and second-gene ration ruthenium metathesis catalysts of 33.4 and 36.9 kcal/mol, respectively. Furthermore a study of the ring-closing metathesis in the second-generation system to liberate norbornene by forming the 14-electron reactive intermediate from the intramolecular pi-complex gives an estimate of the olefin binding energy to the 14-electron complex of around 18 kcal/mol, assuming a loose transition state. The results reported here are in remarkably good agreement with the latest DFT calculations using the M06-L functional.