We study photoinduced metal nitrosyl linkage isomerism in sodium nitroprusside (Na-2[Fe-II(CN)(5)NO]center dot 2H(2)O, SNP) dissolved in methanol using picosecond transient infrared (IR) spectroscopy. The high sensitivity of this technique allows the simultaneous observation of two known metastable (MS) iron-nitrosyl linkage isomers of SNP, [Fe-II(CN)(5)(eta(1)-ON)](2-) (MS1) and [Fe-II(CN)(5)(eta(2)-NO)](2-) (MS2), at room temperature. The transient population of free nitrosyl radicals (NO center dot) is also measured in the sample solution. These three transient species are detected using their distinct nitrosyl stretching frequencies at 1794 cm(-1) (MS1), 1652 cm(-1) (MS2), and 1851 cm(-1) (NO center dot). The metastable isomers and NO are formed on a subpicosecond time scale and have lifetimes greater than 100 ns. A UV (400 nm)-pump power dependence study reveals that MS1 can be formed with one photon, while MS2 requires two photons to be populated at room temperature in solution. Other photodissociation products including cyanide ion, Prussian blue, and [Fe-II(CN)(5)(CH3OH)](2-) are observed. We develop a photochemical kinetic scheme to model our data, and the analysis reveals that photoisomerization and photodissociation of the metal-NO moiety are competing photochemical pathways in SNP dissolved in methanol at room temperature. Based on the analysis, the solvent-associated Fe(III) species and Prussian blue form on a 130 and 320 ps time scale, respectively. The simultaneous detection and characterization of photoinduced linkage isomerism (MS1 and MS2) and photodissociation of the metal-NO bond in SNP highlights the importance of understanding the role played by metastable metal-nitrosyl linkage isomers in the photochemistry of metal-nitrosyl compounds in chemistry and biology.