An infrared study of CO2 activation by holmium ions, Ho+ and HoO+. Issue 37 (15th September 2022)

• Record Type: Journal Article
• Authors: Brewer, Edward I.; Green, Alice E.; Gentleman, Alexander S.; Beardsmore, Peter W.; Pearcy, Philip A. J.; Meizyte, Gabriele; Pickering, Jack; Mackenzie, Stuart R.
• Is Part Of: Physical chemistry chemical physics. Volume 24:Issue 37(2022)
• Page Start: 22716
• Page End: 22723
• Publication Date: 2022-09-15
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d2cp02862j
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : We report a combined experimental and computational study of carbon dioxide activation at gas-phase Ho + and HoO + centres. 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.