Spectroscopic Characterization of a Monomeric, Cyclopentadienyl-Based Rhenium(V) Dioxo Complex

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• 作者：Suresh Raju ; Johann T. B. H. Jastrzebski ; Martin Lutz ; L茅on Witteman ; Johannes R. Dethlefsen ; Peter Fristrup ; Marc-Etienne Moret ; Robertus J. M. Klein Gebbink
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：November 16, 2015
• 年：2015
• 卷：54
• 期：22
• 页码：11031-11036
• 全文大小：346K
• ISSN：1520-510X

文摘

Mononuclear, coordinatively unsaturated rhenium(V) dioxo species of the type XReO₂ (X = Me, substituted cyclopentadienyl) have long been postulated as intermediates in rhenium-catalyzed deoxydehydration, but their characterization was precluded because of aggregation into dimeric or oligomeric structures. Using the bulky 1,2,4-tri-tert-butylcyclopentadienyl (Cp^ttt) ligand, the rhenium(V) dioxo species (Cp^ttt)ReO₂ could now be observed, in equilibrium with the dimeric form [(Cp^ttt)Re(O)渭-O]₂, and characterized by NMR, IR, and UV鈥搗is spectroscopies, as well as electrospray ionization mass spectrometry. (Cp^ttt)ReO₂ is shown to be the primary product of reduction of the rhenium(VII) complex (Cp^ttt)ReO₃ with PPh₃ and demonstrated to react with ethylene glycol significantly faster than its dimeric counterpart, supporting its role as an intermediate in rhenium-catalyzed deoxydehydration reactions.