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Updated: May 1, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Reaction pathways of Rh+ (3F and 1D) with CH3OCH3 in the gas phase
Xiangfeng Chen1, Hoi-sze Yeung, Ning Ding
1Key Laboratory for Applied Technology of Sophisticated Analytical Instruments, Academy of Sciences, Shandong, Jinan, PR China. xiangfchen@yahoo.com.cn
Rationale:
The mass spectrometric studies of transition metal ion-ether reactions are informative in elucidating the principles of metal ion mediated demethanation and dehydrogenation. In order to obtain a deeper understanding of the role of metal ions, it is essential to explore the detailed reaction mechanisms of these reactions, here studied using Rh(+) and dimethyl ether as a model system.
Methods:
The gas-phase demethanation and dehydrogenation pathways of dimethyl ether mediated by Rh(+) ((3)F and (1)D) were investigated by density functional theory in conjunction with the Stuttgart RSC + 6-311 + G(d) basis set. Both singlet and triplet states of reactivity were explored.
Results:
The results indicate that both C-O and C-H bond activation of dimethyl ether mediated by Rh(+) could induce the demethanation reaction. The triplet state demethanation reaction prefers to proceed through C-O bond activation, while the singlet state demethanation channel via C-H bond activation is energetically more favorable. The singlet state dehydrogenation of the ionic product (formaldehyde/Rh(+)) occurs by decomposition of rhodium carbonyl dihydride, while the triplet state dehydrogenation is induced by dissociation of the carbonyl(η(2)-dihydrogen) rhodium species.
Conclusions:
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.
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