Formal oxidative addition of dioxygen to coordinated carbon monoxide. Isolation and characterization of ruthenium carbonate complex of 2-(arylazo)pyridine
| Main Authors: | Ipsita Chatterjee, Pradip Ghosh, Sreebrata Goswami |
|---|---|
| Format: | Article Journal |
| Bahasa: | eng |
| Terbitan: |
, 2015
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| Subjects: | |
| Online Access: |
https://zenodo.org/record/5599233 |
Daftar Isi:
- Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata-700 032, India E-mail : icsg@iacs.res.in The reaction of Ru3(CO)12 with 2,6-dichlorophenylazopyridine (L) in boiling n-octane under positive pressure of di-oxygen affords a blue complex of composition [RuII(CO3)L2]. This reaction exemplifies an unusual chemical transformation wherein the anionic bidentate carbonate, CO3 2 ̄ is formed in situ by formal addition of O2 via activation of coordinated carbon monoxide. The Ru-carbonate complex is characterized by X-ray crystallographic structure analysis nuclear magnetic resonance spectroscopy, cyclic voltammetry, ultraviolet-visible spectroscopy, electron paramagnetic resonance spectroscopy, and density functional theory. The complex displays one reversible electron transfer process at –0.28 V along with two irreversible electron transfer process near –1.23 and 1.42 V. The response at negative potential is due to reduction of the coordinated azo-function. The reversible reductive process is characterized by EPR spectroscopy. Density functional theory calculations have been employed to confirm structural features and to support their spectral and redox properties.