Azaferrocene, (η 5 -C 5 H 5 )(η 5 -C 4 H 4 N)Fe, undergoes a η 5 f η 1 haptotropic shift of the pyrrolyl ligand upon long-wavelength photolysis (λ exc > 495 nm) both in alkane solvents at room temperature and in frozen matrixes at 12 K. Room-temperature photolysis (λ exc > 495 nm) in CO-saturated cyclohexane solution generated (η 5 -C 5 H 5 )(η 1 -N-C 4 H 4 N)Fe(CO) 2 . Irradiation with λ exc ) 532 nm also produced an allyl monocarbonyl species, exo-(η 5 -C 5 H 5 )(η 3 -C-C 4 H 4 N)-Fe(CO), identified by IR spectroscopy. In CO-doped matrixes at 12 K both (η 5 -C 5 H 5 )(η 1 -N-C 4 H 4 N)Fe(CO) and (η 5 -C 5 H 5 )(η 1 -N-C 4 H 4 N)Fe(CO) 2 are formed following broad-band irradiation (λ exc > 495 nm) of (η 5 -C 5 H 5 )(η 5 -C 4 H 4 N)Fe, in a ratio dependent on the concentration of CO in the matrix. Initial irradiation with λ exc ) 538 nm followed by broad-band photolysis (λ exc > 495 nm) in CO-doped matrixes formed additional monocarbonyl species, exo-(η 5 -C 5 H 5 )-(η 3 -C-C 4 H 4 N)Fe(CO), and a species absorbing at 1962 cm -1 , which is either the appropriate endo-isomer or aza-allyl species. Laser flash photolysis experiments of (η 5 -C 5 H 5 )(η 1 -N-C 4 H 4 N)-Fe(CO) 2 in either CO-saturated cyclohexane or toluene produced (η 5 -C 5 H 5 )(η 1 -N-C 4 H 4 N)Fe-(CO), which reacted with CO with rate constants measured at 298 K of (3.0 ( 0.3) × 10 8 and (3.3 ( 0.3) ×10 8 M -1 s -1 , respectively, regenerating (η 5 -C 5 H 5 )(η 1 -N-C 4 H 4 N)Fe(CO) 2 .