Citation: CHEN Qiang, JIANG Li-Xue, LI Hai-Fang, CHEN Jiao-Jiao, ZHAO Yan-Xia, HE Sheng-Gui. Thermal Activation of Methane by Diatomic Vanadium Boride Cations[J]. Acta Physico-Chimica Sinica, ;2019, 35(9): 1014-1020. doi: 10.3866/PKU.WHXB201811039 shu

Thermal Activation of Methane by Diatomic Vanadium Boride Cations

CHEN Qiang ^1,2 ,
JIANG Li-Xue ^1,2,3 ,
LI Hai-Fang ^1,2,3 ,
CHEN Jiao-Jiao ^1,2,3 ,
ZHAO Yan-Xia ^1,2,, ,
HE Sheng-Gui ^1,2,3,,

1.
State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China
2.
Beijing National Laboratory for Molecular Sciences and CAS Research/Education Center of Excellence in Molecular Sciences, Beijing 100190, P. R. China
3.
University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Corresponding author: ZHAO Yan-Xia, chemzyx@iccas.ac.cn HE Sheng-Gui, shengguihe@iccas.ac.cn
Received Date: 28 November 2018
Revised Date: 19 December 2018
Accepted Date: 27 December 2018
Available Online: 3 September 2019
Fund Project: The project was supported by the National Natural Science Foundation of China 21773253Youth Innovation Promotion Association, Chinese Academy of Sciences 2018041China Postdoctoral Science Foundation 2017M611002The project was supported by the National Natural Science Foundation of China (91645203, 21773253), China Postdoctoral Science Foundation(2017M611002), Beijing Natural Science Foundation, China (2182092), and Youth Innovation Promotion Association, Chinese Academy of Sciences(2018041)Beijing Natural Science Foundation, China 2182092The project was supported by the National Natural Science Foundation of China 91645203

Methane activation by transition metal species has been extensively investigated over the past few decades. It is observed that ground-state monocations of bare 3d transition metals are inert toward CH₄ at room temperature because of unfavorable thermodynamics. In contrast, many mono-ligated 3d transition metal cations, such as MO⁺ (M = Mn, Fe, Co, Cu, Zn), MH⁺ (M = Fe, Co), and NiX⁺ (X = H, CH₃, F), as well as several bis-ligated 3d transition metal cations including OCrO⁺, Ni(H)(OH)⁺, and Fe(O)(OH)⁺ activate the C―H bond of methane under thermal collision conditions because of the pronounced ligand effects. In most of the above-mentioned examples, the 3d metal atoms are observed to cooperate with the attached ligands to activate the C―H bond. Compared to the extensive studies on active species comprising of middle and late 3d transition metals, the knowledge about the reactivity of early 3d transition metal species toward methane and the related C―H activation mechanisms are still very limited. Only two early 3d transition metal species HMO⁺ (M = Ti and V) are discovered so far to activate the C―H bond of methane via participation of their metal atoms. In this study, by performing mass spectrometric experiments and density functional theory calculations, we have identified that the diatomic vanadium boride cation (VB⁺) can activate methane to produce a dihydrogen molecule and carbon-boron species under thermal collision conditions. The strong electrostatic interaction makes the reaction preferentially proceed the V side. To generate experimentally observed product ions, a two-state reactivity scenario involving spin conversion from high-spin sextet to low-spin quartet is necessary at the entrance of the reaction. This result is consistent with the reported reactions of 3d transition metal species with CH₄, in which the C―H bond cleavage generally occurs in the low-spin states, even if the ground states of the related active species are in the high-spin states. For VB⁺ + CH₄, the insertion of the synergetic V―B unit (rather than a single V or B atom) into the H₃C―H bond causes the initial C―H bond activation driven by the strong bond strengths of V―CH₃ and B―H. The mechanisms of methane activation by VB⁺ discussed in this study may provide useful guidance to the future studies on methane activation by early transition metal systems.
- Methane activation,
- Early transition metal,
- Boron,
- Mass spectrometry,
- Density functional theory
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