The Reactive Sites of Methane Activation: A Comparison of IrC<sub>3</sub><sup>+</sup> with PtC<sub>3</sub><sup>+</sup>
The activation reactions of methane mediated by metal carbide ions <i>M</i>C<sub>3</sub><sup>+</sup> (<i>M</i> = Ir and Pt) were comparatively studied at room temperature using the techniques of mass spectrometry in conjunction with theoretical calcula...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-10-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/26/19/6028 |
| _version_ | 1797515924913258496 |
|---|---|
| author | Zizhuang Liu Hechen Wu Wei Li Xiaonan Wu |
| author_facet | Zizhuang Liu Hechen Wu Wei Li Xiaonan Wu |
| author_sort | Zizhuang Liu |
| collection | DOAJ |
| description | The activation reactions of methane mediated by metal carbide ions <i>M</i>C<sub>3</sub><sup>+</sup> (<i>M</i> = Ir and Pt) were comparatively studied at room temperature using the techniques of mass spectrometry in conjunction with theoretical calculations. <i>M</i>C<sub>3</sub><sup>+</sup> (<i>M</i> = Ir and Pt) ions reacted with CH<sub>4</sub> at room temperature forming <i>M</i>C<sub>2</sub>H<sub>2</sub><sup>+</sup>/C<sub>2</sub>H<sub>2</sub> and <i>M</i>C<sub>4</sub>H<sub>2</sub><sup>+</sup>/H<sub>2</sub> as the major products for both systems. Besides that, PtC<sub>3</sub><sup>+</sup> could abstract a hydrogen atom from CH<sub>4</sub> to generate PtC<sub>3</sub>H<sup>+</sup>/CH<sub>3</sub>, while IrC<sub>3</sub><sup>+</sup> could not. Quantum chemical calculations showed that the <i>M</i>C<sub>3</sub><sup>+</sup> (<i>M</i> = Ir and Pt) ions have a linear M-C-C-C structure. The first C–H activation took place on the Ir atom for IrC<sub>3</sub><sup>+</sup>. The terminal carbon atom was the reactive site for the first C–H bond activation of PtC<sub>3</sub><sup>+</sup>, which was beneficial to generate PtC<sub>3</sub>H<sup>+</sup>/CH<sub>3</sub>. The orbitals of the different metal influence the selection of the reactive sites for methane activation, which results in the different reaction channels. This study investigates the molecular-level mechanisms of the reactive sites of methane activation. |
| first_indexed | 2024-03-10T06:54:06Z |
| format | Article |
| id | doaj.art-78a8ff742f164f9bad03339ac9ab1b55 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T06:54:06Z |
| publishDate | 2021-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-78a8ff742f164f9bad03339ac9ab1b552023-11-22T16:36:16ZengMDPI AGMolecules1420-30492021-10-012619602810.3390/molecules26196028The Reactive Sites of Methane Activation: A Comparison of IrC<sub>3</sub><sup>+</sup> with PtC<sub>3</sub><sup>+</sup>Zizhuang Liu0Hechen Wu1Wei Li2Xiaonan Wu3Department of Chemistry, Fudan University, Shanghai 200433, ChinaDepartment of Chemistry, Fudan University, Shanghai 200433, ChinaSchool of Mathematics and Physics, North China Electric Power University, Beinong Road 2, Huilongguan, Beijing 102206, ChinaDepartment of Chemistry, Fudan University, Shanghai 200433, ChinaThe activation reactions of methane mediated by metal carbide ions <i>M</i>C<sub>3</sub><sup>+</sup> (<i>M</i> = Ir and Pt) were comparatively studied at room temperature using the techniques of mass spectrometry in conjunction with theoretical calculations. <i>M</i>C<sub>3</sub><sup>+</sup> (<i>M</i> = Ir and Pt) ions reacted with CH<sub>4</sub> at room temperature forming <i>M</i>C<sub>2</sub>H<sub>2</sub><sup>+</sup>/C<sub>2</sub>H<sub>2</sub> and <i>M</i>C<sub>4</sub>H<sub>2</sub><sup>+</sup>/H<sub>2</sub> as the major products for both systems. Besides that, PtC<sub>3</sub><sup>+</sup> could abstract a hydrogen atom from CH<sub>4</sub> to generate PtC<sub>3</sub>H<sup>+</sup>/CH<sub>3</sub>, while IrC<sub>3</sub><sup>+</sup> could not. Quantum chemical calculations showed that the <i>M</i>C<sub>3</sub><sup>+</sup> (<i>M</i> = Ir and Pt) ions have a linear M-C-C-C structure. The first C–H activation took place on the Ir atom for IrC<sub>3</sub><sup>+</sup>. The terminal carbon atom was the reactive site for the first C–H bond activation of PtC<sub>3</sub><sup>+</sup>, which was beneficial to generate PtC<sub>3</sub>H<sup>+</sup>/CH<sub>3</sub>. The orbitals of the different metal influence the selection of the reactive sites for methane activation, which results in the different reaction channels. This study investigates the molecular-level mechanisms of the reactive sites of methane activation.https://www.mdpi.com/1420-3049/26/19/6028mthane activationmass spectrometryquantum chemical calculationractive site |
| spellingShingle | Zizhuang Liu Hechen Wu Wei Li Xiaonan Wu The Reactive Sites of Methane Activation: A Comparison of IrC<sub>3</sub><sup>+</sup> with PtC<sub>3</sub><sup>+</sup> Molecules mthane activation mass spectrometry quantum chemical calculation ractive site |
| title | The Reactive Sites of Methane Activation: A Comparison of IrC<sub>3</sub><sup>+</sup> with PtC<sub>3</sub><sup>+</sup> |
| title_full | The Reactive Sites of Methane Activation: A Comparison of IrC<sub>3</sub><sup>+</sup> with PtC<sub>3</sub><sup>+</sup> |
| title_fullStr | The Reactive Sites of Methane Activation: A Comparison of IrC<sub>3</sub><sup>+</sup> with PtC<sub>3</sub><sup>+</sup> |
| title_full_unstemmed | The Reactive Sites of Methane Activation: A Comparison of IrC<sub>3</sub><sup>+</sup> with PtC<sub>3</sub><sup>+</sup> |
| title_short | The Reactive Sites of Methane Activation: A Comparison of IrC<sub>3</sub><sup>+</sup> with PtC<sub>3</sub><sup>+</sup> |
| title_sort | reactive sites of methane activation a comparison of irc sub 3 sub sup sup with ptc sub 3 sub sup sup |
| topic | mthane activation mass spectrometry quantum chemical calculation ractive site |
| url | https://www.mdpi.com/1420-3049/26/19/6028 |
| work_keys_str_mv | AT zizhuangliu thereactivesitesofmethaneactivationacomparisonofircsub3subsupsupwithptcsub3subsupsup AT hechenwu thereactivesitesofmethaneactivationacomparisonofircsub3subsupsupwithptcsub3subsupsup AT weili thereactivesitesofmethaneactivationacomparisonofircsub3subsupsupwithptcsub3subsupsup AT xiaonanwu thereactivesitesofmethaneactivationacomparisonofircsub3subsupsupwithptcsub3subsupsup AT zizhuangliu reactivesitesofmethaneactivationacomparisonofircsub3subsupsupwithptcsub3subsupsup AT hechenwu reactivesitesofmethaneactivationacomparisonofircsub3subsupsupwithptcsub3subsupsup AT weili reactivesitesofmethaneactivationacomparisonofircsub3subsupsupwithptcsub3subsupsup AT xiaonanwu reactivesitesofmethaneactivationacomparisonofircsub3subsupsupwithptcsub3subsupsup |