An infrared study of CO2 activation by holmium ions, Ho+ and HoO.
Phys Chem Chem Phys
; 24(37): 22716-22723, 2022 Sep 28.
Article
in En
| MEDLINE
| ID: mdl-36106954
ABSTRACT
We report a combined experimental and computational study of carbon dioxide activation at gas-phase Ho+ and HoO+ centres. Infrared action spectra of Ho(CO2)n+ and [HoO(CO2)n]+ ion-molecule complexes have been recorded in the spectral region 1700-2400 cm-1 and assigned by comparison with simulated spectra of energetically low-lying structures determined by density functional theory. Little by way of activation is observed in Ho(CO2)n+ complexes with CO2 binding end-on to the Ho+ ion. By contrast, all [HoO(CO2)n]+ complexes n ≥ 3 show unambiguous evidence for formation of a carbonate radical anion moiety, . The signature of this structure, a new vibrational band observed around 1840 cm-1 for n = 3, continues to red-shift monotonically with each successive CO2 ligand binding with net charge transfer from the ligand rather than the metal centre.
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MEDLINE
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En
Year:
2022
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Article