title: Reexamining Oxidation States during the Synthesis of 2-Rhodaoxetanes from Olefins.
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.
authors.affiliation: Department of Chemistry, The University of British Columbia , Vancouver, British Columbia V6T 1Z1, Canada.
authors.forename: Addison N
authors.initials: AN
authors.lastname: Desnoyer
authors.affiliation: Department of Chemistry, The University of British Columbia , Vancouver, British Columbia V6T 1Z1, Canada.
authors.forename: Shirin
authors.initials: S
authors.lastname: Behyan
authors.affiliation: Department of Chemistry, The University of British Columbia , Vancouver, British Columbia V6T 1Z1, Canada.
authors.forename: Brian O
authors.initials: BO
authors.lastname: Patrick
authors.affiliation: Department of Chemistry, The University of British Columbia , Vancouver, British Columbia V6T 1Z1, Canada.
authors.forename: Alexander
authors.initials: A
authors.lastname: Dauth
authors.affiliation: Department of Chemistry, The University of British Columbia , Vancouver, British Columbia V6T 1Z1, Canada.
authors.forename: Jennifer A
authors.initials: JA
authors.lastname: Love
authors.affiliation: Department of Chemistry, The University of British Columbia , Vancouver, British Columbia V6T 1Z1, Canada.
authors.forename: Pierre
authors.initials: P
authors.lastname: Kennepohl