钒硼双原子阳离子活化甲烷研究

doi:10.3866/PKU.WHXB201811039

物理化学学报 >> 2019, Vol. 35 >> Issue (9): 1014-1020.doi: 10.3866/PKU.WHXB201811039

所属专题：碳氢键活化

钒硼双原子阳离子活化甲烷研究

陈强^1,²,姜利学^1,^2,³,李海方^1,^2,³,陈娇娇^1,^2,³,赵艳霞^1,^2,*(),何圣贵^1,^2,^3,*()

¹ 中国科学院化学研究所，分子动态与稳态结构国家重点实验室，北京 100190
² 北京分子科学国家研究中心；中国科学院分子科学科教融合卓越创新中心, 北京 100190
³ 中国科学院大学，北京 100049

收稿日期:2018-11-28 录用日期:2018-12-27 发布日期:2019-01-03
通讯作者: 赵艳霞,何圣贵 E-mail:chemzyx@iccas.ac.cn;shengguihe@iccas.ac.cn
基金资助:
国家自然科学基金(91645203);国家自然科学基金(21773253);中国博士后科学基金(2017M611002);北京市自然科学基金(2182092);中国科学院青年创新促进会基金(2018041)

Thermal Activation of Methane by Diatomic Vanadium Boride Cations

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

Received:2018-11-28 Accepted:2018-12-27 Published:2019-01-03
Contact: Yan-Xia ZHAO,Sheng-Gui HE E-mail:chemzyx@iccas.ac.cn;shengguihe@iccas.ac.cn
Supported by:
The project was supported by the National Natural Science Foundation of China(91645203);The project was supported by the National Natural Science Foundation of China(21773253);China Postdoctoral Science Foundation(2017M611002);Beijing Natural Science Foundation, China(2182092);Youth Innovation Promotion Association, Chinese Academy of Sciences(2018041)

摘要/Abstract

摘要：

3d过渡金属物种活化甲烷的研究已有较多报道，但人们对3d前过渡金属物种与甲烷反应体系的报道非常少，与之相关的甲烷活化机理的认识仍然非常有限。在本工作中，我们通过气相质谱实验和密度泛函理论计算证实了VB⁺离子可以在热碰撞条件下活化甲烷产生氢气和碳硼化合物，由于强的静电相互作用，甲烷活化优先发生在VB⁺离子的V原子位点。甲烷的活化转化涉及二态反应性，在反应的入口处需要经历从高自旋六重态到低自旋四重态的自旋反转。由于V―CH₃以及B―H化学键较强，H₃C―H键断裂以V―B单元协同插入而非单个V或B原子插入C―H键的方式进行。对VB⁺活化甲烷的机理认识可以为新型3d过渡金属催化剂活化甲烷的研究提供理论基础。

关键词: 甲烷活化, 前过渡金属, 硼, 质谱, 密度泛函理论

Abstract:

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.

Key words: Methane activation, Early transition metal, Boron, Mass spectrometry, Density functional theory

MSC2000:

O643

陈强,姜利学,李海方,陈娇娇,赵艳霞,何圣贵. 钒硼双原子阳离子活化甲烷研究[J]. 物理化学学报, 2019, 35(9): 1014-1020.

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

图/表 4

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钒硼双原子阳离子活化甲烷研究

Thermal Activation of Methane by Diatomic Vanadium Boride Cations

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