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Reexamining Oxidation States during the Synthesis of 2-Rhodaoxetanes from Olefins

TitleReexamining Oxidation States during the Synthesis of 2-Rhodaoxetanes from Olefins
Publication TypeJournal Article
Year of Publication2016
AuthorsDesnoyer, AN, Behyan, S, Patrick, BO, Dauth, A, Love, JA, Kennepohl, P
JournalInorganic Chemistry
Volume55
Pagination13-15
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.

URLhttp://dx.doi.org/10.1021/acs.inorgchem.5b02703
DOI10.1021/acs.inorgchem.5b02703