TY - JOUR
T1 - Ethyltrioxorhenium – Catalytic application and decomposition pathways
AU - Hofmann, Benjamin J.
AU - Huber, Stefan
AU - Reich, Robert M.
AU - Drees, Markus
AU - Kühn, Fritz E.
PY - 2019/4
Y1 - 2019/4
N2 - Despite its sensitivity, ethyltrioxorhenium (ETO) is applicable as catalyst in the epoxidation of olefins using either tert-butylhydroperoxide (TBHP) or hydrogen peroxide as oxidants. Conversions of approximately 80% with only epoxide being formed and a turnover frequency (TOF) of up to 1200 h−1 can be achieved with TBHP in 1,1,1,3,3,3-hexafluroroisopropanol (HFI). As proven for its more stable congener MTO, the active species is highly likely an alkyl peroxo species, as shown by 17O-NMR experiments. Experimental and theoretical studies on the decomposition mechanism of ETO in diluted polar solvents reveal that the degradation pathway proceeds equally via β-hydrogen elimination and radical decomposition.
AB - Despite its sensitivity, ethyltrioxorhenium (ETO) is applicable as catalyst in the epoxidation of olefins using either tert-butylhydroperoxide (TBHP) or hydrogen peroxide as oxidants. Conversions of approximately 80% with only epoxide being formed and a turnover frequency (TOF) of up to 1200 h−1 can be achieved with TBHP in 1,1,1,3,3,3-hexafluroroisopropanol (HFI). As proven for its more stable congener MTO, the active species is highly likely an alkyl peroxo species, as shown by 17O-NMR experiments. Experimental and theoretical studies on the decomposition mechanism of ETO in diluted polar solvents reveal that the degradation pathway proceeds equally via β-hydrogen elimination and radical decomposition.
UR - http://dx.doi.org/10.1016/j.jorganchem.2019.02.004
U2 - 10.1016/j.jorganchem.2019.02.004
DO - 10.1016/j.jorganchem.2019.02.004
M3 - Article
VL - 885
SP - 32
EP - 38
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
ER -