Generation of reactive species by one-electron reduction of fischer-type carbene complexes of group 6 metals and their use for carbon-carbon bond formation

Kohei Fuchibe; Nobuharu Iwasawa

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Generation of reactive species by one-electron reduction of fischer-type carbene complexes of group 6 metals and their use for carbon-carbon bond formation

机译：通过单电子还原第6类金属的菲舍尔型卡宾配合物生成反应性物种及其在碳-碳键形成中的用途

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Carbon-carbon bond-forming reactions mediated by one-electron reduction of Fischer-type carbene complexes of Group 6 metals were investigated. In the case of aryl - or silylcarbene complexes of tungsten, the anion radical species generated by one-electron reduction smoothyl underwent addition reaction to ethyl acrylate. One-electron reduction of alpha,beta-unsaturated carbene complexes afforded biscarbene complexes by dimerization of the corresponding anion radical species at the position gamma to the metal center. In contrast, one-electron reduction of chromium phenyl-or alkylcarbene complexes gave, via carbonyl insertion, alpha-methoxyacylchromate complexes, which further underwent conjugate addition to various electron-poor olefins to give the corresponding alpha-methoxyketones.

机译：研究了由第6组金属的Fischer型卡宾配合物的单电子还原介导的碳-碳键形成反应。在钨的芳基-或甲硅烷基碳烯络合物的情况下，由单电子还原平滑烷基产生的阴离子自由基种类与丙烯酸乙酯进行加成反应。 α，β-不饱和卡宾配合物的单电子还原通过在相对于金属中心的位置γ处将相应的阴离子基团二聚而得到双卡宾配合物。相反，铬-苯基或烷基碳烯络合物的单电子还原通过羰基插入产生α-甲氧基酰基铬酸酯络合物，其进一步共轭加成到各种贫电子的烯烃中以得到相应的α-甲氧基酮。

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《Chemistry: A European journal》 |2003年第4期|共10页
作者
Kohei Fuchibe; Nobuharu Iwasawa;
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正文语种 eng
中图分类化学;应用化学;
关键词
carbene ligands; chromium; radical ions; reduction; tungsten;

机译：卡宾配体铬自由基离子还原钨;

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专利

1. Generation of reactive species by one-electron reduction of fischer-type carbene complexes of group 6 metals and their use for carbon-carbon bond formation [J] . Kohei Fuchibe, Nobuharu Iwasawa Chemistry: A European journal . 2003,第4期

机译：通过单电子还原第6类金属的菲舍尔型卡宾配合物生成反应性物种及其在碳-碳键形成中的用途
2. Carbon-Silicon and Carbon-Carbon Bond Formation by Elimination Reactions at Metal N-Heterocyclic Carbene Complexes [J] . Polly L. Arnold, Zoee R. Turner, Ronan Bellabarba, Journal of the American Chemical Society . 2011,第30期

机译：在金属N-杂环碳配合物中通过消除反应形成碳-硅和碳-碳键
3. Critical Effect of Phosphane Ligands on the Mechanism of Carbon-Carbon Bond Formation Involving Palladium(II)Complexes:A Theoretical Investigation of Reductive Elimination from Square-Planar and T-Shaped Species [J] . Valentine P.Ananikov, Djamaladdin G.Musaev, Keiji Morokuma European journal of inorganic chemistry . 2007,第34期

机译：磷配体对涉及钯（II）配合物的碳-碳键形成机理的临界效应：正方形和T型物种还原消除的理论研究
4. Construction of Carbon Skeleton by Metathesis of Fischer-type Chromium Carbene Complexes with Alkynes Containing Silyl Enol Ether Moiety [C] . Sotai Wada, Toshimichi Asakura, Nobuharu Iwasawa Symposium on Organometallic Chemistry . 2004

机译：用含甲硅烷基烯醇醚部分的炔烃型铬卡宾络合物复分解碳骨架施工碳骨架
5. Reactions of metal carbonyl anions and Fischer-type transition metal carbene complexes: An investigation of the different sites of nucleophilic attack on Fischer carbenes. [D] . Toomey, Laurence Michael. 1997

机译：羰基金属阴离子与Fischer型过渡金属卡宾配合物的反应：对Fischer carbenes进行亲核攻击的不同位点的研究。
6. Heterobimetallic Pd–K carbene complexes via one-electron reductions of palladium radical carbenes [O] . Peng Cui, Melissa R. Hoffbauer, Mariya Vyushkova, 2016

机译：通过单电子还原钯基碳酸盐的异双金属Pd–K卡宾络合物
7. Carbon-carbon bond forming reactions from bis(carbene)-platinum(II) complexes and olefin polymerization and oligomerization using group 4 post-metallocene complexesud [O] . Klet Rachel Christine 2014

机译：双（卡宾） - 铂（II）配合物的碳 - 碳键形成反应和烯烃聚合和低聚反应使用第4族后茂金属配合物 ud
8. Chemistry of Polynuclear Metal Complexes with Bridging Carbene or Carbyne Ligands. Part 90. (1) Synthesis of the Complexes (W2M2(mu-CO)(mu-CMe)(mu3-CMe)-(Mu-PPh2)2(CO)3(eta-C5H5)2) (M = Rh or Ir) and Related Tetra- and Penta-nuclear Metal Compounds: Interconversion of Ketenyl and Lambda(5) -Phospha-alkyne Ligands Bridging Tungsten-Rhodium Bonds. [R] . Davies, S. J., Stone, F. G. 1989

机译：具有桥接卡宾或卡宾配体的多核金属配合物的化学。部分90.（1）配合物的合成（W2m2（mu-CO）（mu-Cme）（mu3-Cme） - （mu-pph2）2（CO）3（eta-C5H5）2）（m = Rh或Ir）和相关的四核和五核金属化合物：Ketenyl和Lambda（5）-phospha-alkyne配体桥联钨 - 铑键的相互转化。

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Generation of reactive species by one-electron reduction of fischer-type carbene complexes of group 6 metals and their use for carbon-carbon bond formation

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