Kinetic isotope effects for nonadiabatic proton transfer reactions in a polar environment. 1. Interpretation of tunneling kinetic isotopic effects

Kiefer PM; Hynes JT

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Kinetic isotope effects for nonadiabatic proton transfer reactions in a polar environment. 1. Interpretation of tunneling kinetic isotopic effects

机译：极性环境中非绝热质子转移反应的动力学同位素效应。 1.解释隧道动力学同位素效应

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A theoretical study of primary kinetic isotope effects (KIEs) is presented for proton transfer (PT) reactions in a polar environment in the nonadiabatic, i.e., tunneling, regime. This treatment differs from traditional descriptions for PT most notably in the identification of a solvent coordinate as the reaction coordinate. The theory explicitly addresses KIE features that are extremely sensitive to the proton donor-proton acceptor mode dynamics. Besides KIE behaviors that are not consistent with nontunneling PT, individual KIE aspects in some cases, such as magnitude, temperature dependence, variation with reaction asymmetry, and Swain-Schaad behavior can yield results consistent with nontunneling PT. However, a combination of KIE aspects-with particular emphasis on KIE variation with reaction asymmetry or temperature-can clearly identify tunneling in PT systems. In addition, PT via excited proton vibrational states is shown to significantly contribute to the reaction rate and KIEs, especially for extremely asymmetric reactions, where it can dominate.

机译：提出了在绝热（即隧穿）状态下在极性环境中质子转移（PT）反应的主要动力学同位素效应（KIE）的理论研究。这种处理与传统的PT描述不同，最明显的是将溶剂坐标确定为反应坐标。该理论明确地解决了对质子供体-质子受体模式动力学极为敏感的KIE特征。除了与非隧道PT不一致的KIE行为外，在某些情况下，各个KIE方面（例如幅度，温度依赖性，反应不对称性的变化以及Swain-Schaad行为）都可以产生与非隧道PT一致的结果。但是，结合KIE方面-特别强调KIE变化与反应不对称或温度-可以清楚地识别PT系统中的隧穿。此外，PT通过激发的质子振动态被证明对反应速率和KIE有显着贡献，特别是对于极不对称的反应，PT可以占优势。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2004年第52期|共16页
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Kiefer PM; Hynes JT;
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COUPLED ELECTRON-TRANSFER; FREE-ENERGY RELATIONS; RADICAL-ION PAIR; TRANSFER-REACTION-RATES; TRANSFER RATE CONSTANTS; ENZYME CATALYSIS; HYDRIDE-TRANSFER; HYDROGEN-ATOM; DIHYDROFOLATE-REDUCTASE; ALCOHOL-DEHYDROGENASE;

机译：耦合电子转移;自由能关系;自由基离子对;转移反应速率;转移速率常数;酶催化;氢化物转移;氢原子;二氢叶酸还原酶;醇脱水;

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1. Kinetic isotope effects for nonadiabatic proton transfer reactions in a polar environment. 1. Interpretation of tunneling kinetic isotopic effects [J] . Kiefer PM, Hynes JT The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2004,第52期

机译：极性环境中非绝热质子转移反应的动力学同位素效应。 1.解释隧道动力学同位素效应
2. Steric Effects on the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Hydride Transfer Reactions in Solution: Caused by the Isotopically Different Tunneling Ready State Conformations? [J] . Binita Maharjan, Mahdi Raghibi Boroujeni, Jonathan Lefton, Journal of the American Chemical Society . 2015,第20期

机译：溶液中氢化物转移反应中的二级动力学同位素效应对一级同位素依赖性的立体效应：由同位素不同的隧穿就绪态构型引起？
3. Computational Replication of the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Solution Hydride-Transfer Reactions: Supporting the Isotopically Different Tunneling Ready State Conformations [J] . Derakhshani-Molayousefi Mortaza, Kashefolgheta Sadra, Eilers James E., The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2016,第25期

机译：溶液氢化物转移反应中次级动力学同位素效应的主要同位素依赖性的计算复制：支持同位素不同的隧穿就绪态构象
4. Kinetic and Equilibrium Deuterium Isotope Effects for C-H Bond Reductive Elimination and Oxidative Addition Reactions Involving the Ansa-Tungstenocene Methyl-Hydride Complex Me_2Si(C_5Me_4)_2W(Me)H [C] . Kevin E. Janak, David G. Churchill, Gerard parkin American Chemical Society National Meeting . 2004

机译：动力学和均衡氘同位素对C-H键的减少消除和氧化添加反应涉及Ansa-钨烯甲基 - 氢化物复合物ME_2SI（C_5ME_4）_2 W（ME）H.
5. Enthalpy and Entropy in Chemical Reactivity: I. Temperature Dependence of Secondary Deuterium Isotope Effects on the Acidity of Carboxylic Acids and Phenols, and a Rejection of any Inductive Contribution II. Kinetic and Mechanistic Studies of Reactions of Malonic Anhydrides III. Developing an ITC Method to Measure Heats of Proton Transfer [D] . Flach, Agnes 2012

机译：化学反应的焓和熵：I.次级氘同位素的温度依赖性对羧酸和苯酚酸度的影响，以及任何感应贡献的抑制II。丙二酸酐反应的动力学和机理研究。开发用于测量质子传递热的ITC方法
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机译：通过大豆脂脂氧基酶的C-H切割反应中的次要动力学同位素效应来研究内部球体重组：在基板骨架中的隧穿以及转移的氢气
7. Isotope Effects in Proton-transfer Reactions. VIII. Isotope Effects in the Proton-transfer from (--)-Menthone to Methoxide Ion in Methanol and Methanol--Dimethyl Sulfoxide Solutions. [O] . Bo Anhede, Lars Baltzer, Nils-Åke Bergman, 1982

机译：质子转移反应中的同位素作用。 VIII。在甲醇和甲醇 - 二甲基亚甲醚溶液中的（ - ） - 晶体中对甲醇离子的质子转移的同位素效应。
8. Ab Initio Predictions and Experimental Confirmation of Large Tunneling Contributions to Rate Constants and Kinetic Isotope Effects for Hydrogen Atom Transfer Reactions [R] . Garrett, B. C., Truhlar, D. G., Bowman, J. M., 1986

机译：大型隧道对速率常数的贡献和氢原子转移反应的动力学同位素效应的从头算预测和实验证实

Kinetic isotope effects for nonadiabatic proton transfer reactions in a polar environment. 1. Interpretation of tunneling kinetic isotopic effects

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