IR spectroscopic characterization of products of methane and cyclopropane activation by Ru cations

IF 1.6 3区化学 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

International Journal of Mass Spectrometry Pub Date : 2023-10-19 DOI:10.1016/j.ijms.2023.117165

Frank J. Wensink , Deepak Pradeep , P.B. Armentrout , Joost M. Bakker

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引用次数: 1

Abstract

Methane and cyclopropane (c-C₃H₆) were reacted with Ru⁺ ions in a room temperature ion trap and the resulting products were identified using a combination of mass spectrometry, IR action spectroscopy, and density functional theory calculations. In the reaction with methane, no products with odd numbers of carbon atoms were located, whereas significant amounts of products with even numbers of carbon atoms were observed. We identified [Ru,2C,4H]⁺ as the Ru⁺ ion with an ethene ligand attached, and [Ru,4C,6H]⁺ as a Ru(η⁴-cis-1,3-butadiene)⁺ complex. The barrier toward formation of Ru(C₂H₄)⁺ + 2H₂ was calculated at the B3LYP/def2-TZVPPD level to be 0.80 eV above the energy of the ground state Ru⁺ (⁴F) + 2 CH₄ reactants. In the reaction of c-C₃H₆ with Ru⁺, we identified the dehydrogenation product [Ru,3C,4H]⁺ as Ru(η²-propyne)⁺, [Ru,2C,2H]⁺ as Ru⁺ with an ethyne ligand, and [Ru,5C,5H]⁺ as Ru(η⁵-c-C₅H₅)⁺ having a cyclopentadienyl ligand.

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Ru离子活化甲烷和环丙烷产物的红外光谱表征

甲烷和环丙烷(c-C3H6)在室温离子阱中与Ru+离子反应，结合质谱、红外光谱和密度泛函理论计算对产物进行了鉴定。在与甲烷的反应中，没有发现奇数碳原子的产物，而观察到大量的偶数碳原子的产物。我们鉴定出[Ru,2C,4H]+为带有乙烯配体的Ru+离子，[Ru,4C,6H]+为Ru(η - 4-顺-1,3-丁二烯)+络合物。在B3LYP/def2-TZVPPD水平上，Ru(C2H4)+ + 2H2的形成势垒比Ru+ (4F) + 2ch4反应物的基态能量高0.80 eV。c-C3H6俄文+的反应中,我们确定了脱氢产物[俄文、3 c, 4 h] +俄罗斯(η2-propyne) +[俄文,2 c 2 h] +跑步+乙炔配体,和[俄文5 c 5 h] +俄罗斯(η5-c-C5H5) +环戊二烯基配体。

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来源期刊

International Journal of Mass Spectrometry 物理-光谱学

CiteScore

3.60

自引率

5.60%

发文量

145

审稿时长

71 days

期刊介绍： The journal invites papers that advance the field of mass spectrometry by exploring fundamental aspects of ion processes using both the experimental and theoretical approaches, developing new instrumentation and experimental strategies for chemical analysis using mass spectrometry, developing new computational strategies for data interpretation and integration, reporting new applications of mass spectrometry and hyphenated techniques in biology, chemistry, geology, and physics. Papers, in which standard mass spectrometry techniques are used for analysis will not be considered. IJMS publishes full-length articles, short communications, reviews, and feature articles including young scientist features.