C-H vs C-C Bond Activation of Acetonitrile and Benzonitrile via Oxidative Addition: Rhodium vs Nickel and Cp~* vs Tp' (Tp' = Hydrotris(3,5-dimethylpyrazol-1-yl)borate, Cp~* = η~5-Pentamethylcyclopentadienyl)

Meagan E. Evans; Ting Li; William D. Jones

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C-H vs C-C Bond Activation of Acetonitrile and Benzonitrile via Oxidative Addition: Rhodium vs Nickel and Cp~* vs Tp' (Tp' = Hydrotris(3,5-dimethylpyrazol-1-yl)borate, Cp~* = η~5-Pentamethylcyclopentadienyl)

机译：CH与CC通过氧化加成反应活化乙腈和苯甲腈：铑vs镍，Cp〜* vs Tp'（Tp'=氢三（3,5-二甲基吡唑-1-基）硼酸酯，Cp〜* =η〜5-五甲基环戊二烯基）

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The photochemical reaction of (C_5Me_5)Rh(PMe_3)H_2 (1) in neat acetonitrile leads to formation of the C-H activation product, (C_5Me_5)Rh(PMe_3)(CH_2CN)H (2). Thermolysis of this product in acetonitrile or benzene leads to thermal rearrangement to the C-C activation product, (C_5Me_5)Rh(PMe_3)(CH_3)(CN) (4). Similar results were observed for the reaction of 1 with benzonitrile. The photolysis of 1 in neat benzonitrile results in C-H activation at the ortho, meta, and para positions. Thermolysis of the mixture in neat benzonitrile results in clean conversion to the C-C activation product, (C_5Me_5)Rh(PMe_3)(C_6H_5)(CN) (5). DFT calculations on the acetonitrile system show the barrier to C-H activation to be 4.3 kcal mol~(-1) lower than the barrier to C-C activation. A high-energy intermediate was also located and found to connect the transition states leading to C-H and C-C activation. This intermediate has an agostic hydrogen interaction with the rhodium center. Reactions of acetonitrile and benzonitrile with the fragment [Tp'Rh(CNneopentyl)] show only C-H and no C-C activation. These reactions with rhodium are compared and contrasted to related reactions with [Ni(dippe)H]_2, which show only C-CN bond cleavage.

机译：（C_5Me_5）Rh（PMe_3）H_2（1）在纯乙腈中的光化学反应导致形成C-H活化产物（C_5Me_5）Rh（PMe_3）（CH_2CN）H（2）。该产物在乙腈或苯中的热解导致热重排为C-C活化产物（C_5Me_5）Rh（PMe_3）（CH_3）（CN）（4）。 1与苄腈的反应观察到相似的结果。净苄腈中1的光解作用导致邻位，间位和对位的C-H活化。混合物在纯苯甲腈中的热解可将其干净转化为C-C活化产物（C_5Me_5）Rh（PMe_3）（C_6H_5）（CN）（5）。在乙腈体系上的DFT计算表明，对C-H活化的障碍比对C-C活化的障碍低4.3 kcal mol〜（-1）。还找到了高能中间体，发现该中间体连接导致C-H和C-C活化的过渡态。该中间体与铑中心具有有害的氢相互作用。乙腈和苄腈与片段[Tp'Rh（CNneopentyl）]的反应显示仅C-H，没有C-C活化。比较了与铑的这些反应，并将其与[Ni（dippe）H] _2的相关反应进行了对比，后者仅显示了C-CN键的裂解。

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来源
《Journal of the American Chemical Society》 |2010年第45期|p.16278-16284|共7页
作者
Meagan E. Evans; Ting Li; William D. Jones;
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Department of Chemistry, University of Rochester, Rochester, New York 14627, United States;

Department of Chemistry, University of Rochester, Rochester, New York 14627, United States;

Department of Chemistry, University of Rochester, Rochester, New York 14627, United States;

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收录信息美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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1. C−H vs C−C Bond Activation of Acetonitrile and Benzonitrile via Oxidative Addition: Rhodium vs Nickel and Cp* vs Tp′ (Tp′ = Hydrotris(3,5-dimethylpyrazol-1-yl)borate, Cp* = η5-Pentamethylcyclopentadienyl) [J] . Meagan E. Evans Ting Li and William D. Jones American Chemical Society . 2010,第45期

机译：乙腈和苯甲腈通过氧化加成的CH键与C键的活化：铑vs镍键和Cp * vs Tp'（Tp'=氢三（3,5-二甲基吡唑-1-基）硼酸酯，Cp * =η5-五甲基五甲基环戊二烯基）
2. Preparation of chalcogenolato-bridged dinuclear Tp*Rh-Cp*Ru complexes (Tp* = hydrotris(3,5-dimethylpyrazol-l-yl)borate,Cp* eta~5-pentamethylcyclopentadienyl) and binding of dioxygen to their Ru sites [J] . Shoken Nagao, Hidetake Seine, Masanobu Hidai, Dalton transactions: An international journal of inorganic chemistry . 2005,第19期

机译：硫属元素桥联双核Tp * Rh-Cp * Ru络合物的制备（Tp * =氢三（3,5-二甲基吡唑-1-基）硼酸酯，Cp * eta〜5-五甲基环戊二烯基）并将双氧结合到其Ru位上
3. Rhodium complexes with hydrotris(3-p-anisylpyrazol-1-yl)borate ligand Tp(pAn). Intramolecular C-H bond activation and dehydro-chlorination processes [J] . Santa Maria MD., Campo JA., Cano M., Journal of Organometallic Chemistry . 2000,第1期

机译：铑与氢三（3-对茴香基吡唑-1-基）硼酸酯配体Tp（pAn）形成络合物。分子内C-H键活化和脱氯化氢过程
4. C-H Bond Activation by Iridium and Rhodium Complexes: Catalytic Hydrogen-Deuterium Exchange and C-C Bond-Forming Reactions [C] . Steven R. Klei, Klan L. Tan, Jeffrey T. Golden, American Chemical Society National Meeting . 2004

机译：铱和铑配合物的C-H键活化：催化氢 - 氘交换和C-C键形成反应
5. Cp*Ir Complexes Relevant to C-H Activation and Oxidation Reactions. [D] . Lehman, Matthew C. 2014

机译：与C-H活化和氧化反应有关的Cp * Ir配合物。
6. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation [O] . Denise A. Colby, Robert G. Bergman, Jonathan A. Ellman -1

机译：经由杂原子的定向C-H键活化铑催化的C-C键的形成
7. Cobalt(II) Complexes with N,N,N-Scorpionates and Bidentate Ligands: Comparison of Hydrotris(3,5-dimethylpyrazol-1-yl)borate Tp* vs. Phenyltris(4,4-dimethyloxazolin-2-yl)borate ToM to Control the Structural Properties and Reactivities of Cobalt Centers [O] . Toshiki Nishiura, Takahiro Uramoto, Yuichiro Takiyama, 2018

机译：钴（II）钴（II）与N，N，N-蝎子和二齿配体的复合物：Hydrotris（3,5-二甲基吡唑-1-基）的比较硼酸盐Tp *与苯基三（4,4-二甲基唑嗪-2-基）硼酸盐汤姆控制钴中心的结构性和反应

C-H vs C-C Bond Activation of Acetonitrile and Benzonitrile via Oxidative Addition: Rhodium vs Nickel and Cp~* vs Tp' (Tp' = Hydrotris(3,5-dimethylpyrazol-1-yl)borate, Cp~* = η~5-Pentamethylcyclopentadienyl)

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