Identification of an “End-on” Nickel−Superoxo Adduct, [Ni(tmc)(O2)]

Identification of an “End-on” Nickel−Superoxo Adduct, [Ni(tmc)(O2)]

An “end-on” Ni2+−superoxo adduct has been prepared via two independent synthetic routes and its structure ascertained by spectroscopic and computational methods. The new structure type in nickel coordination chemistry is supported by resonance Raman and EPR spectroscopic features, the former display...

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Veröffentlicht in:Journal of the American Chemical Society 2006-11, Vol.128 (44), p.14230-14231
Hauptverfasser: Kieber-Emmons, Matthew T., Annaraj, Jamespandi, Seo, Mi Sook, Van Heuvelen, Katherine M., Tosha, Takehiko, Kitagawa, Teizo, Brunold, Thomas C., Nam, Wonwoo, Riordan, Charles G.
Format: Artikel
Sprache:eng
Schlagworte:
ADDUCTS
Chemistry
ELECTRON SPIN RESONANCE
Exact sciences and technology
General and physical chemistry
Heterocyclic Compounds - chemistry
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Molecular Structure
MORPHOLOGY
Nickel - chemistry
NICKEL COMPLEXES
Organometallic Compounds - chemistry
OXIDIZERS
Oxygen - chemistry
RAMAN SPECTROSCOPY
Spectrum Analysis, Raman
Superoxides - chemistry
SYNTHESIS
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Beschreibung
Zusammenfassung:An “end-on” Ni2+−superoxo adduct has been prepared via two independent synthetic routes and its structure ascertained by spectroscopic and computational methods. The new structure type in nickel coordination chemistry is supported by resonance Raman and EPR spectroscopic features, the former displaying a high frequency ν (O−O) mode (1131 cm-1) consistent with significant superoxo character. The Ni2+−superoxo adduct oxidizes PPh3 to OPPh3 in quantitative yield.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0644879