期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 24, 期 37, 页码 22716-22723出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2cp02862j
关键词
-
资金
- EPSRC [EP/T021675]
- Somerville College, Oxford
- AEG
- Worcester College
In this study, carbon dioxide activation at gas-phase Ho+ and HoO+ centers was investigated through experimental and computational methods. The results showed that Ho(CO2)(n)(+) complexes with CO2 binding end-on to the Ho+ ion did not undergo significant activation, while [HoO(CO2)(n)](+) complexes with n >= 3 provided clear evidence for the formation of a carbonate radical anion.
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, {CO3 center dot delta-}. 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 Eigand binding with net charge transfer from the Eigand rather than the metal centre.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据