Variations of the organometallic cluster known as King’s complex, [(C5H5)Fe(CO)]4, have been synthesized to study the excited-state transition responsible for reverse saturable absorption observed at 532 nm in this molecule. Picosecond pump-probe measurements have been used to measure the excited-state cross sections and lifetimes in King’s complex and the analogs methyl-King’s complex, [CH3(C5H4)Fe(CO)]4, and triethylaluminum King’s complex, [(C5H5) Fe{COAl(C2H5)3}]4. Within experimental error, the excited-state parameters are unaffected by alterations to either the carbonyl or the cyclopentadienyl ligand of the King’s complex. These results are consistent with an excited-state absorption resulting from a second d to d transition within the singlet states of the metal core.