An experimental study of the mechanism for the combined CO and CH bond activation of dimethylether by bare Fe+ ions

Ion–Molecule Reactions of “Rollover” Cyclometalated [Pt(bipy−H)]+ (bipy=2,2′‐bipyridine) with Dimethyl Ether in Comparison with Dimethyl Sulfide: An Experimental/Computational Study

“…[21] Computations: In the computational studies we employed the Gaussian 03 program package [22] using basis sets of approximately triple-x quality. For H, C, N, O, and S atoms these were the triple-x plus polarization basis sets (TZVP) of Ahlrichs and co-workers.…”

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

“…4(a)), is similar to those in previous analogous demethanation reactions mediated by 4 Fe + and 2 Ni + . [12] The analogous tricoordinated species H-M + (CH 3 )-OCH 2 , which was found in the reaction of 6 Fe + with DME, [12] is, however, not involved as a stable intermediate here. Energetically, 3 TS 2-4 is 2.3 kcal/mol lower than the separate reactants.…”

“…[3,4] Previous experiments revealed that M + (M = Fe and Ni) can activate dimethyl ether (DME) to generate the formaldehyde/M + complex and methane as the ionic product and neutral product, respectively. [5][6][7][8][9][10] In addition to the demethanation reaction, the second row transition metal ions can induce the dehydrogenation of DME. For example, the demethanation and dehydrogenation of DME were observed in the reaction of Rh + with DME in an ion-beam experiment.…”

“…With regard to the metal ion mediated demethanation mechanism, Schwarz and co-workers proposed that the C-O bond activation was the rate-determining step, which was followed by hydrogen transfer from the insertion intermediate [CH 3 -M-OCH 3 ] + to the demethanation product complex [CH 4 -M-OCH 2 ] + . [6] Theoretically, Wang et al investigated the Ti + -mediated C-O bond activation of DME and compared the energetics of CH 3 migration and H atom transfer. [12] Recently, we reported the density functional theory (DFT) results of Fe + -( 4 F and 6 D) and Ni + -mediated demethanation of DME.…”

Gas‐phase reaction mechanism of Pd+ with CH3CHO: A density functional theoretical study

“…With regard to small oxygencontaining molecules, the gas-phase reactions of aldehydes, ketones, and ethers with different metal ions have been widely investigated [6][7][8][9][10][11][12][13]. Previous experimental studies involved the use of Fourier transform ion cyclotron resonance and ionbeam experiments by Beauchamp, Schwarz, and Freiser [6][7][8][9][10][11]. These experimental results, along with the thermodynamic information from others indicated that demethanation of acetaldehyde by late transition metal ions is a dominant channel at low reaction energies.…”