Theoretical study of the mechanism of two successive N-methylene C-H bond activations on a phosphine-tethered N-heterocyclic carbene on a triruthenium carbonyl cluster

Yan Jing; Han Zhe; Zhang Dongju; Liu Chengbu

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Theoretical study of the mechanism of two successive N-methylene C-H bond activations on a phosphine-tethered N-heterocyclic carbene on a triruthenium carbonyl cluster

机译：三种亚甲基C-H键活化对三羰基羰基亚杂环膦酰基杂环的机理的理论研究

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Recently the Kennedy group reported a unique successive N-methylene C-H bond activation on N-heterocyclic triruthenium carbene complexes. Here, density functional theory calculations have been performed on this reaction to clarify the molecular-level mechanism of the two C-H bond activations. The calculated results indicated that the reaction occurs sequentially through the following steps: phosphine ligand dissociation from the Ru center followed by rearrangement of ligands on Ru center, the first C-H bond oxidative addition to Ru, the elimination of the first CO ligand with recoordination of the phosphine ligand, the second CO ligand elimination followed by the second C-H bond activation, and hydride migrations between Ru centers. The rate-determining step is the first C-H bond activation, which needs to overcome a barrier of 37.9 kcal mol(-1).

机译：最近，肯尼迪集团在N-杂环苯甲酸酯上报道了一种独特的连续N-亚甲基C-H键活化。这里，已经对该反应进行了密度函数理论计算，以阐明两个C-H键活化的分子水平机制。计算结果表明，通过以下步骤顺序地发生反应：从Ru中心的膦配体解离，然后重新排列Ru中心的配体，第一个CH键氧化加入ru，在重新配录中消除了第一Co配体的消除膦配体，第二CO配体消除，然后是第二CH键活化，并在RU中心之间的氢化物迁移。速率确定步骤是第一个C-H键活化，其需要克服37.9kcal摩尔（-1）的屏障。

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《RSC Advances》 |2016年第102期|共6页
作者
Yan Jing; Han Zhe; Zhang Dongju; Liu Chengbu;
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Shandong Univ Minist Educ Inst Theoret Chem Key Lab Colloid &

Interface Chem Jinan 250100 Peoples R China;

New Mat Inst Shandong Acad Sci Jinan 250014 Peoples R China;

Shandong Univ Minist Educ Inst Theoret Chem Key Lab Colloid &

Interface Chem Jinan 250100 Peoples R China;

Shandong Univ Minist Educ Inst Theoret Chem Key Lab Colloid &

Interface Chem Jinan 250100 Peoples R China;

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正文语种 eng
中图分类化学;
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1. Theoretical study of the mechanism of two successive N-methylene C-H bond activations on a phosphine-tethered N-heterocyclic carbene on a triruthenium carbonyl cluster [J] . Yan Jing, Han Zhe, Zhang Dongju, RSC Advances . 2016,第102期

机译：三种亚甲基C-H键活化对三羰基羰基亚杂环膦酰基杂环的机理的理论研究
2. Mechanism of the sequential activation of two C-H bonds of a NHC N-methyl group on a triruthenium carbonyl cluster [J] . Yan Jing, Han Zhe, Zhang Dongju, Theoretical chemistry accounts . 2015,第11期

机译：三钌羰基簇上NHC N-甲基的两个C-H键顺序活化的机理
3. Double C-H bond activation of an NHCN-methyl group on triruthenium and triosmium carbonyl clusters: A DFT mechanistic study [J] . Cabeza JA, Perez-Carreno E Organometallics . 2008,第18期

机译：三钌和三os羰基簇上NHCN-甲基的双C-H键活化：DFT机理研究
4. G-H Bond Activation of Arenes Mediated by Coordinatively Unsaturated Cp*Fe Complexes of N-Heterocyclic Carbene [C] . Tsubasa Hatanaka, Yasuhiro Ohki, Kazuyuki Tatsumi Symposium on Organometallic Chemistry . 2008

机译：通过协调不饱和CP * Fe复合物介导的N-杂环酯介导的G-H键活化
5. Mechanisms of electron transfer and hydrogen activation in selected triruthenium clusters with multiple bridging ligands. Part I. The attenuation of radical reactivity in triruthenium trihydrido(alkylidyne) clusters. Electrochemistry and kinetics of decomposition of the 47-electron cluster radical, via a disproportionation path. Part II. The activation of molecular hydrogen at transition metal centers via kinetics and mechanism of reversible oxidative addition of hydrogen across the metal-metal bond of (mu-hydrogen)(2)Ruthenium(3)(Carbon monoxide)(8)(mu-phosphorus(t-BU)(2))(2). [D] . Bierdeman, David John. 2000

机译：具有多个桥联配体的选定三钌簇中电子转移和氢活化的机理。第一部分。三氢三钌（亚烷基）簇中自由基反应性的减弱。通过歧化路径分解47电子簇自由基的电化学和动力学。第二部分通过（mu-hydrogen）（2）钌（3）（一氧化碳）（8）（mu-phosphorus（）的金属-金属键上氢的可逆氧化加成反应的动力学和机理激活过渡金属中心的分子氢t-BU）（2））（2）。
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7. Synthesis of New Iridium N-Heterocyclic Carbene Complexes and Facile Intramolecular Alkyl C-H Bond Activation Reactions of the Carbene Ligand [O] . -1

机译：新铱N-杂环卡宾配合物的合成及Carbene配体的体分子内烷基C-H键活化反应
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机译：卤甲基金属化合物。 LVII。将苯基（溴二氯甲基）汞衍生的二氯卡宾插入C-H键中。 β-金属活化C-H插入反应的进一步研究。

Theoretical study of the mechanism of two successive N-methylene C-H bond activations on a phosphine-tethered N-heterocyclic carbene on a triruthenium carbonyl cluster

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