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Reactions of Laser-Ablated Scandium Atoms with Dioxygen. Infrared Spectra of ScO, OScO, (O 2 )ScO, (ScO) 2 , and Sc(O 2 ) 2 in Solid Argon

1997; American Chemical Society; Volume: 101; Issue: 48 Linguagem: Inglês

10.1021/jp972482f

1520-5215

George V. Chertihin, Lester Andrews, Marzio Rosi, Charles W. Bauschlicher,

Catalytic Processes in Materials Science

Laser-ablated Sc atoms react with O2 during condensation in excess argon to give ScO, OScO, and (O2)ScO as major products, which are identified from oxygen isotopic substitution on their matrix infrared spectra. The linear suboxide molecule ScOSc is a minor product. Annealing allows further association to form ScO3, (ScO)2, and Sc(O2)2. The OScO molecule is bent: based on the oxygen-18 shift in the ν3 mode, the valence angle is 128 ± 4°. The ν3 fundamental of OScO at 722 cm-1 is substantially lower than the ScO fundamental at 976 cm-1, which is in accord with weaker bonds in the dioxide. Similar reactions in excess nitrogen give evidence of extensive ligation.