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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Gas-Phase Oxidation of Isomeric Butenes and Small Alkanes by Vanadium-Oxide and -Hydroxide Cluster Cations
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Gas-Phase Oxidation of Isomeric Butenes and Small Alkanes by Vanadium-Oxide and -Hydroxide Cluster Cations

机译：钒氧化物和羟基氧化物簇阳离子对异丁烯和小烷烃的气相氧化

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摘要

Bare vanadium-oxide and -hydroxide cluster cations (V_mO_nH_0~+,m=2-4,n= 1 -10,o - 0,1) were generated by electrospray ionization in order to examine their intrinsic reactivity toward isomeric butenes and small alkanes using mass spectrometric techniques.Two of the major reactions described here concern the activation of C-H bonds of the alkene/alkane substrates resulting in the transfer of two hydrogen atoms and/or attachment of the dehydrogenated hydrocarbon to the cluster cations;these processes are classified as oxidative dehydrogenation (ODH) and dehydrogenation,respectively.For the dehydrogenation of butene,it evolved as a general trend that high-valent clusters prefer ODH resulting in the addition of two hydrogen atoms to the cluster concomitant with elimination of neutral butadiene,whereas low-valent clusters tend to add the diene with parallel loss of molecular hydrogen.Deuterium labeling experiments suggest the operation of a different reaction mechanism for V_2O_2~+ and V_4O_(10)~+ compared to the other cluster cations investigated,and these two cluster cations also are the only ones of the vanadium-oxide ions examined here that are able to dehydrogenate small alkanes.The kinetic isotope effects observed experimentally imply an electron transfer mechanism for the ion-molecule reactions of the alkanes with V_4O_(10)~+.
机译：通过电喷雾电离产生了钒氧化物和氢氧根氧化物簇阳离子（V_mO_nH_0〜+，m = 2-4，n = 1 -10，o-0,1），以检查它们对异构丁烯和小烷烃的固有反应此处描述的两个主要反应涉及烯烃/烷烃底物的CH键的活化，导致两个氢原子的转移和/或脱氢烃与簇状阳离子的附着;这些过程分为氧化脱氢（ODH）和脱氢分别。对于丁烯的脱氢，一般趋势是高价团簇偏爱ODH，导致向团簇中添加两个氢原子，同时消除了中性丁二烯，而低-价簇趋向于加成二烯而使分子氢平行损失。氘标记实验表明，V_2O_2〜+和V_4O反应机理不同_（10）〜+与其他被研究的簇状阳离子相比，这两个簇状阳离子也是这里所考察的唯一能够使小烷烃脱氢的钒氧化物离子。实验观察到的动力学同位素效应暗示了电子转移V_4O_（10）〜+与烷烃发生离子分子反应的机理

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