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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Gas-Phase Reactions of Transition-Metal Ions with Hexafluorobenzene: Room-Temperature Kinetics and Periodicities in Reactivity
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Gas-Phase Reactions of Transition-Metal Ions with Hexafluorobenzene: Room-Temperature Kinetics and Periodicities in Reactivity

机译：过渡金属离子与六氟苯的气相反应：室温动力学和反应周期

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摘要

An inductively coupled plasma (ICP) selected-ion flow tube tandem mass spectrometer has been employed in a systematic survey of room-temperature reactions of C_6F_6 with 29 transition-metal ions. The atomic ions were produced at ca. 5500 K in an ICP source and were allowed to decay radiatively and to thermalize by collisions with Ar and He atoms prior to reaction, although for some atomic ions, this quenching may be incomplete. Rate coefficients and product distributions were measured for the reactions of first-row atomic ions from Sc~+ to Zn~+, of second-row atomic ions from Y~+ to Cd~+ (excluding Tc~+), and of third-row atomic ions from La~+ to Hg~+. Marked differences were observed for reactivities of early and late transition metal cations with regard to both the reaction efficiency and the type of reaction pathway. Remarkable multiple (up to four) fluorine atom abstraction, proceeding close to the collision rate, dominated the chemistry observed with early transition metal cations while simple association of up to two molecules of C_6F_6 to the metal cation dominated the chemistry of late transition metal cations. Correlations were found between the electronic configuration of the metal cation and the nature of the reaction path and the reaction efficiency. Only the early third-row Hf~+, Ta~+, and W~+ transition-metal ions exhibited some C-C and C-F bond-dissociation channels leading to ring cleavage.
机译：电感耦合等离子体（ICP）选择离子流管串联质谱仪已用于C_6F_6与29种过渡金属离子的室温反应的系统研究。原子离子的产生温度约为在ICP源中5500 K，并在反应之前通过与Ar和He原子的碰撞使其辐射衰减并热化，尽管对于某些原子离子而言，这种淬灭可能是不完全的。测量了第一行原子离子从Sc〜+到Zn〜+，第二行原子离子从Y〜+到Cd〜+（不包括Tc〜+）和第三行原子的反应的速率系数和产物分布。从La〜+到Hg〜+排列原子离子。在反应效率和反应途径类型方面，观察到早期和晚期过渡金属阳离子的反应性存在明显差异。接近碰撞速率的大量（最多四个）氟原子抽象化，在早期过渡金属阳离子的化学反应中占主导地位，而最多两个C_6F_6分子与金属阳离子的简单缔合则在后期过渡金属阳离子的化学反应中占主导地位。发现金属阳离子的电子构型与反应路径的性质和反应效率之间存在相关性。只有早期的第三行Hf〜+，Ta〜+和W〜+过渡金属离子显示出一些C-C和C-F键解离通道，从而导致环断裂。

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