The photodissociations of two metal nitrosyl compounds, Co(CO)(3)NO and Mn(CO)(4)NO, were studied at 450 nm, in the metal-to-nitrosyl charge-transfer region for both compounds. The rotational distributions of free NO in the upsilon " = 0 vibrational state were determined by laser-induced fluorescence excitation. A Surprisal Analysis shows that the NO population distributions display a dynamical bias toward lower rotation in both compounds. The similarity between the NO rotational distributions is surprising, considering that Co(CO)(3)NO was expected to dissociate through a bent transition state and Mn(CO)(4)NO was not. The spin-orbit populations of the NO products ((2)Pi (1/2) and (2)Pi (3/2)) are equally populated in both compounds, indicating that the electronic surfaces that produce these two states are strongly coupled at the transition state. An upper limit of the M-NO bond dissociation energy is estimated at 52 kcal/mol from the rotational assignments.