Reaction pathways of Rh⁺ (³F and ¹D) with CH₃OCH₃ in the gas phase

Abstract

Based on the results, it is believed that the demethanation reaction of dimethyl ether mediated by transition metal monocation would preferably occur through the C-O bond activation pathway. Combined with previous studies, a general reaction mechanism of the transition metal monocation with dimethyl ether is proposed.

Analysis of the Pressure and Temperature Dependence of the Complex-Forming Bimolecular Reaction CH3OCH3 + Fe+

“…The specific rate constants could all be represented in the form of eq A3 of the Appendix with the parameter s* ≈ 5. 5. The relevant well depths, also required for the calculation of k(E), were taken as that for 6 1 (mechanism a and c) and for 4 1 (mechanism b).…”

“…The gas phase reactions of transition metal cations with dimethyl ether, CH 3 OCH 3 , have frequently been used as a prototype for the activation of CO bonds in organic molecules (see, e.g., refs − ). Depending upon the reaction conditions, one has the possibility of adduct formation or demethanation.…”

“…Figure5. Modeled specific rate constants k(E) for the processes6 1 → 6 TS 1−2 → ••• (curve a), 4 1 → 4 TS 1−2 → ••• (curve b),6 1 → 6 TS 3′-3 → ••• (curve c), and 6 1→ Fe + + CH 3 OCH 3 (curve d); RRKM calculations with parameters from the Supporting Information).…”

Oxidative Cleavage of the β-O-4 Linkage of Lignin by Transition Metals: Catalytic Properties and the Performance of Density Functionals

“…Previous computational and experimental studies that addressed reactions encompassing ethers and TM atoms or ions showed that the reaction of C–O bond cleavage begins with the TM binding to the oxygen atom of the ether, forming an adduct. Following an intermediate structural arrangement, the reaction terminates with hydrogen migration. − Figure shows a possible reaction pathway for methoxyethane activation, which is similar to the mechanism outlined in the ether and TM ions studies . The metal atom first binds to the oxygen atom of methoxyethane to form the adduct [MO­(CH 3 CH 2 )­(CH 3 )].…”

“…The Minnesota functionals (M06 and M06L) were considered due to the inclusion of spin kinetic energy, and their parametrization includes a number of TM species. B3LYP was selected due to its wide use and its utility in the prediction of TM compound geometries, 27 whereas PBE0, the other hybrid-GGA functional, was chosen because it performed well in a study on the C−O bond cleavage of dimethyl ether by TM ions. 29 The final functional, B2PLYP, is a double-hybrid-GGA functional and includes the nonlocal correlation energy predicted at the level of second-order many body perturbation theory.…”