当前位置：
X-MOL 学术
›
J. Phys. Chem. A
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Calorimetric Study of the Activation of Hydrogen by Tris(pentafluorophenyl)borane and Trimesitylphosphine
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-11-09 00:00:00 , DOI: 10.1021/acs.jpca.7b08582 Adrian Y. Houghton 1 , Tom Autrey 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-11-09 00:00:00 , DOI: 10.1021/acs.jpca.7b08582 Adrian Y. Houghton 1 , Tom Autrey 1
Affiliation
|
The mechanism of H2 heterolysis by the frustrated Lewis pair of B(C6F5)3 and P(mes)3 was investigated by isothermal reaction calorimetry in the temperature range from 30 to 90 °C. The experimental heat curves were modeled in Berkeley Madonna to obtain both kinetic and thermodynamics data simultaneously. The H2 activation reaction is treated as a single, termolecular step with a rate constant of 0.61 M–2 s–1 at 303 K with an exothermic enthalpy of reaction, ΔHH2 = −141 kJ/mol. An Eyring analysis gave activation parameters of ΔH‡ = 13.6(9) kJ mol–1 and ΔS‡ = −204(85) J K–1 mol–1. Using D2 gas in place of H2 gas provided an opportunity to measure the relative rates of D2 versus H2 heterolysis to yield a the kinetic isotope effect, KIE = 1.1(1).
中文翻译：
三（五氟苯基）硼烷和三甲苯基膦活化氢的量热研究
通过等温反应量热法在30至90°C的温度范围内研究了沮丧的B（C 6 F 5）3和P（mes）3的Lewis对引起的H 2杂化机理。在伯克利·麦当娜（Berkeley Madonna）中对实验热曲线进行建模，以同时获得动力学和热力学数据。为H 2活化反应被视为具有0.61微米的速率常数的单一，三分子步骤-2小号-1在303 K的反应的放热焓，Δ ħ ħ 2 = -141千焦/摩尔。Eyring分析给出了激活参数ΔH ‡= 13.6（9）kJ mol –1和ΔS ‡ = −204（85）JK –1 mol –1。使用D 2气体代替H 2气体提供了一个机会来测量D 2与H 2杂解的相对速率，以产生动力学同位素效应，KIE = 1.1（1）。
更新日期：2017-11-09
中文翻译：
三（五氟苯基）硼烷和三甲苯基膦活化氢的量热研究
通过等温反应量热法在30至90°C的温度范围内研究了沮丧的B（C 6 F 5）3和P（mes）3的Lewis对引起的H 2杂化机理。在伯克利·麦当娜（Berkeley Madonna）中对实验热曲线进行建模，以同时获得动力学和热力学数据。为H 2活化反应被视为具有0.61微米的速率常数的单一，三分子步骤-2小号-1在303 K的反应的放热焓，Δ ħ ħ 2 = -141千焦/摩尔。Eyring分析给出了激活参数ΔH ‡= 13.6（9）kJ mol –1和ΔS ‡ = −204（85）JK –1 mol –1。使用D 2气体代替H 2气体提供了一个机会来测量D 2与H 2杂解的相对速率，以产生动力学同位素效应，KIE = 1.1（1）。
京公网安备 11010802027423号