Synthesis and Characterization of Cationic Rhodium Peroxo Complexes

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• 作者：Judy Cipot-Wechsler ; Danielle Covelli ; Jeremy M. Praetorius ; Nigel Hearns ; Olena V. Zenkina ; Eric C. Keske ; Ruiyao Wang ; Pierre Kennepohl ; Cathleen M. Crudden
• 刊名：Organometallics
• 出版年：2012
• 出版时间：November 12, 2012
• 年：2012
• 卷：31
• 期：21
• 页码：7306-7315
• 全文大小：570K
• 年卷期：v.31,no.21(November 12, 2012)
• ISSN：1520-6041

文摘

Mononuclear cationic rhodium complexes of dioxygen have been synthesized and characterized. Crystallographic, spectroscopic, and computational results support the conclusion that these complexes are best described as Rh^III{O₂^{2鈥?/sup>} (rhodium(III) peroxo) complexes, in contrast to recently reported neutral analogues that are best described as RhI{1O₂} adducts. The nature of the ligand trans to the O₂ ligand is crucial in defining the electronic nature of the RhO₂ bonding. It is determined that 蟺-donor ligands such as the halides鈥攊n conjunction with sufficient steric bulk鈥攃an stabilize the formation of RhI{1O₂} adducts, whereas stronger field ligands lead to the stabilization of asymmetric O₂ binding that ultimately favors formation of higher coordinate RhIII peroxo species. The factors that control the relative stabilization of RhIII{O₂2鈥?/sup>} versus RhI{1O₂} species are related to the well-established Dewar鈥揅hatt鈥揇uncanson model that has been successfully used to describe the bonding in isoelectronic transition-metal alkene complexes. The specific factors that control the stabilization of one electromer (resonance structure) over another are explored and discussed in detail.}