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, L.
AU - Dethlefsen, Johannes R.
AU - Fristrup, Peter
AU - Moret, Marc Etienne
AU - Klein Gebbink, Bert
PY - 2015/11/16
Y1 - 2015/11/16
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.
UR - http://www.scopus.com/inward/record.url?scp=84947551849&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.5b02366
DO - 10.1021/acs.inorgchem.5b02366
M3 - Article
AN - SCOPUS:84947551849
SN - 0020-1669
VL - 54
SP - 11031
EP - 11036
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 22
ER -