TY - JOUR
T1 - Theoretical Investigation of the Gas-Phase Reaction of CrO+ with Propane
AU - Beck, Jennifer E.
AU - Dudley, Timothy J.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/3/2
Y1 - 2017/3/2
N2 - Transition metal oxide cations (e.g., MO+) have been shown to oxidize small alkanes in the gas phase. The chromium oxide cation is of particular interest because it is more reactive than oxides of earlier transition metals but is more selective than oxides of later transition metals. The reaction of CrO+ with propane has been shown to produce a number of products: propanol, propene, ethene, and hydrogen. Few theoretical studies exist for reactions of simple transition metal oxide cations with larger alkanes. We have analyzed the potential energy surfaces associated with the reaction of CrO+ with propane using two DFT methods, B3LYP and M06-L. Energetically viable reaction paths leading to each experimentally observed product have been characterized. Each reaction path begins with formation of a reactive intermediate in which either an α- or β-hydrogen from propane is extracted by the oxygen atom of CrO+. While pathways leading to formation of hydrogen and ethene were found to occur on a single spin surface, energetically viable pathways to forming propanol and propene require a transition from the quartet spin surface to the sextet surface. The minimum-energy crossing points between the quartet and sextet surfaces were found to be well below the energy level of the reactants and structurally resemble the initial reactive intermediates. (Figure Presented).
AB - Transition metal oxide cations (e.g., MO+) have been shown to oxidize small alkanes in the gas phase. The chromium oxide cation is of particular interest because it is more reactive than oxides of earlier transition metals but is more selective than oxides of later transition metals. The reaction of CrO+ with propane has been shown to produce a number of products: propanol, propene, ethene, and hydrogen. Few theoretical studies exist for reactions of simple transition metal oxide cations with larger alkanes. We have analyzed the potential energy surfaces associated with the reaction of CrO+ with propane using two DFT methods, B3LYP and M06-L. Energetically viable reaction paths leading to each experimentally observed product have been characterized. Each reaction path begins with formation of a reactive intermediate in which either an α- or β-hydrogen from propane is extracted by the oxygen atom of CrO+. While pathways leading to formation of hydrogen and ethene were found to occur on a single spin surface, energetically viable pathways to forming propanol and propene require a transition from the quartet spin surface to the sextet surface. The minimum-energy crossing points between the quartet and sextet surfaces were found to be well below the energy level of the reactants and structurally resemble the initial reactive intermediates. (Figure Presented).
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U2 - 10.1021/acs.jpca.6b10909
DO - 10.1021/acs.jpca.6b10909
M3 - Article
C2 - 28198621
AN - SCOPUS:85027281947
SN - 1089-5639
VL - 121
SP - 1715
EP - 1725
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 8
ER -