@article { ISI:000367706100005, title = {Reexamining Oxidation States during the Synthesis of 2-Rhodaoxetanes from Olefins}, journal = {Inorg. Chem.}, volume = {55}, number = {1}, year = {2016}, month = {JAN 4}, pages = {13-15}, 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(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.

}, issn = {0020-1669}, doi = {10.1021/acs.inorgchem.5b02703}, author = {Desnoyer, Addison N. and Behyan, Shirin and Patrick, Brian O. and Dauth, Alexander and Love, Jennifer A. and Kennepohl, Pierre} }