TY - JOUR
T1 - Spectroscopic Characterization of a Monomeric, Cyclopentadienyl-Based Rhenium(V) Dioxo Complex
AU - Raju, Suresh
AU - Jastrzebski, Johann T. B. H.
AU - Lutz, Martin
AU - Witteman, Léon
AU - Dethlefsen, Johannes Rytter
AU - Fristrup, Peter
AU - Moret, Marc-Etienne
AU - Gebbink, Robertus J. M. Klein
N1 - 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.
PY - 2015
Y1 - 2015
N2 - 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.
AB - 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.
U2 - 10.1021/acs.inorgchem.5b02366
DO - 10.1021/acs.inorgchem.5b02366
M3 - Journal article
C2 - 26517008
SN - 0020-1669
VL - 54
SP - 11031
EP - 11036
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 22
ER -