Femtosecond mid-infrared excitation of room temperature W(CO)(6)/n-hexane solutions resonant with the T-1u CO-stretching mode transfers vibrational population to at least v = 6. The population distribution in levels v = 0 to v = 5 was measured by transient infrared absorption spectroscopy. Resonance frequencies, anharmonic shifts and spectral broadening of observed ladder transitions were also characterized. Populating v = 6 deposits similar to12000 cm(-1) in a single mode which is close to the dissociation energy of one W-C bond. These results constitute a significant step toward initiation and ultimate control of condensed phase, mid-infrared induced ground state reactions relevant to practical synthetic transformations. (C) 2004 Elsevier B.V. All rights reserved.