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

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• 作者：Addison N. Desnoyer ; Shirin Behyan ; Brian O. Patrick ; Alexander Dauth ; Jennifer A. Love ; Pierre Kennepohl
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：January 4, 2016
• 年：2016
• 卷：55
• 期：1
• 页码：13-15
• 全文大小：266K
• ISSN：1520-510X

文摘

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.