Reexamining Oxidation States during the Synthesis of 2-Rhodaoxetanes from Olefins.
Inorg Chem
; 55(1): 13-5, 2016 Jan 04.
Article
em En
| MEDLINE
| ID: mdl-26670683
ABSTRACT
Herein, we report experimental, spectroscopic, and computational data that indicate that a rhodium ethylene complex, formally described as rhodium(I) and which forms a 2-rhoda(III) oxetane following reaction with H2O2, is more accurately described as a rhodium(III) metallacyclopropane. X-ray absorption spectroscopy clearly demonstrates a change in the oxidation state at rhodium following ligand coordination with tris(2-pyridylmethyl)amine. Both NMR and density functional theory studies suggest a high energy barrier to rotation of the coordinated ethylene, which is attributed to large geometric and electronic reorganization resulting from the loss of π-back-bonding. These results imply that the role of H2O2 in the formation of 2-rhoda(III) oxetanes is to oxidize the C2H4 fragment rather than the metal center, as has been previously suggested.
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01-internacional
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MEDLINE
Idioma:
En
Ano de publicação:
2016
Tipo de documento:
Article