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

Suresh Raju, Johann T. B. H. Jastrzebski, Martin Lutz, Léon Witteman, Johannes Rytter Dethlefsen, Peter Fristrup, Marc-Etienne Moret, Robertus J. M. Klein Gebbink

Research output: Contribution to journalJournal articleResearchpeer-review

271 Downloads (Pure)

Abstract

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 (Cpttt) ligand, the rhenium(V) dioxo species (Cpttt)ReO2 could now be observed, in equilibrium with the dimeric form [(Cpttt)Re(O)μ-O]2, and characterized by NMR, IR, and UV-vis spectroscopies, as well as electrospray ionization mass spectrometry. (Cpttt)ReO2 is shown to be the primary product of reduction of the rhenium(VII) complex (Cpttt)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.
Original languageEnglish
JournalInorganic Chemistry
Volume54
Issue number22
Pages (from-to)11031-11036
Number of pages6
ISSN0020-1669
DOIs
Publication statusPublished - 2015

Bibliographical note

This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

Fingerprint Dive into the research topics of 'Spectroscopic Characterization of a Monomeric, Cyclopentadienyl-Based Rhenium(V) Dioxo Complex'. Together they form a unique fingerprint.

Cite this