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Population relaxation of CO(v = 1 ) vibrations in solution phase metal carbonyl complexes

✍ Scribed by E.J. Heilweil; R.R. Cavanagh; J.C. Stephenson

Publisher: Elsevier Science
Year: 1987
Tongue: English
Weight: 791 KB
Volume: 134
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(87)87118-x

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✦ Synopsis

Picosecond infrared saturation-recovery experiments were performed to obtain measurements of the vibrational energy lifetimes ( r, ) of CO( v= 1) vibrations (Y GZ 1920-l 985 cm-' ) of carbonyl-containing metal complexes in dilute, room-temperature solutions. For relaxation of the F,, CO-stretching vibration of W( CO), in CCL, CHCls, n-hexane and benzene, T, was found to be T, = 800f 200, 480f 50, 140 k 15 and 60f 6 ps, respectively, while the same mode of Cr(C0)6 in these solvents gave T, ~440 f 70, 295 f 30, 145 f 25 and 59 k 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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