Abstract
Picosecond infrared saturation-recovery experiments were performed to obtain measurements of the vibrational energy lifetimes ( T 1) of CO( v = 1) vibrations ( v≈ 1920-1985 cm −1) of carbonyl-containing metal complexes in dilute, room-temperature solutions. For relaxation of the F 1u CO-stretching vibration of W(CO) 6 in CCl 4, CHCl 3, n-hexane and benzene, T 1, was found to be T 1 = 800±200, 480±50, 140±15 and 60±6 ps, respectively, while the same mode of Cr(CO) 6, in these solvents gave T 1 = 440±70, 295±30, 145±25 and 59±6 ps. Monocarbonyl complexes with coordinated triphenylphosphine groups (TPP) have shorter CO( v = 1 ) lifetimes. These observations are rationalized in terms of molecular structure, intramolecular bonding, solvent interaction, and energy accepting vibrational modes.
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