Title | Reexamining Oxidation States during the Synthesis of 2-Rhodaoxetanes from Olefins |
Publication Type | Journal Article |
Year of Publication | 2016 |
Authors | Desnoyer, AN, Behyan, S, Patrick, BO, Dauth, A, Love, JA, Kennepohl, P |
Journal | Inorg. Chem. |
Volume | 55 |
Pagination | 13-15 |
Date Published | JAN 4 |
ISSN | 0020-1669 |
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(111) metallacydopropane. 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 pi-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. |
DOI | 10.1021/acs.inorgchem.5b02703 |