键合作用以及静电在高价有机铜化合物中推动 C-C 键形成中的作用。
Bonding and the role of electrostatics in driving C-C bond formation in high valent organocopper compounds.
机构信息
Department of Chemistry, Trinity University, San Antonio, Texas 78212-7200, USA.
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, 162 Sciences Drive, Ithaca, NY 14853, USA.
出版信息
Chem Commun (Camb). 2022 Dec 22;59(1):98-101. doi: 10.1039/d2cc05865k.
Abstract
The electronic structures and contrasting reactivity of [Cu(CF)] and [Cu(CF)(CH)] were probed using coupled cluster and valence bond calculations. The Cu-C bonds in these complexes were found to be charge shift bonds. A key finding is that electrostatics likely prevent [Cu(CF)] from accessing a productive transition state for C-C bond formation while promote one for [Cu(CF)(CH)]. These results therefore highlight essential design criteria for Cu-mediated C-C/C-heteroatom bond formation.
摘要
使用耦合簇和价键计算方法研究了[Cu(CF₅)]和[Cu(CF₅)(CH₃)]的电子结构和对比反应性。这些配合物中的 Cu-C 键被发现是电荷转移键。一个关键的发现是，静电作用可能阻止[Cu(CF₅)]进入有利于 C-C 键形成的有效过渡态，而有利于[Cu(CF₅)(CH₃)]。因此，这些结果突出了铜介导的 C-C/C-杂原子键形成的基本设计标准。
相似文献
1
Bonding and the role of electrostatics in driving C-C bond formation in high valent organocopper compounds.键合作用以及静电在高价有机铜化合物中推动 C-C 键形成中的作用。
Chem Commun (Camb). 2022 Dec 22;59(1):98-101. doi: 10.1039/d2cc05865k.
2
Unraveling the Chemistry of High Valent Arylcopper Compounds and Their Roles in Copper-Catalyzed Arene C-H Bond Transformations Using Synthetic Macrocycles.解析高价芳基铜化合物的化学性质及其在使用合成大环配体的铜催化芳基 C-H 键转化反应中的作用。
Acc Chem Res. 2022 Oct 4;55(19):2796-2810. doi: 10.1021/acs.accounts.2c00316. Epub 2022 Aug 22.
3
An Organocopper(III) Fluoride Triggering C-CF Bond Formation.一种引发碳-碳氟键形成的有机铜（III）氟化物。
Angew Chem Int Ed Engl. 2024 Mar 11;63(11):e202319412. doi: 10.1002/anie.202319412. Epub 2024 Jan 22.
4
Direct Arene Trifluoromethylation Enabled by a High-Valent Cu -CF Compound.高价铜-CF 化合物促进的直接芳环三氟甲基化反应。
Angew Chem Int Ed Engl. 2022 Oct 4;61(40):e202209029. doi: 10.1002/anie.202209029. Epub 2022 Aug 29.
5
Csp-Csp Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes.Csp-Csp 键形成的由确定结构的铜（III）配合物引发的还原消除反应。
J Am Chem Soc. 2019 Feb 20;141(7):3153-3159. doi: 10.1021/jacs.8b12632. Epub 2019 Feb 6.
6
The structure and chemical bonding in the N(2)-CuX and N(2)...XCu (X = F, Cl, Br) systems studied by means of the molecular orbital and Quantum Chemical Topology methods.通过分子轨道和量子化学拓扑方法研究的N₂-CuX和N₂...XCu（X = F、Cl、Br）体系中的结构和化学键。
J Comput Chem. 2008 Dec;29(16):2677-92. doi: 10.1002/jcc.21010.
7
Organocopper(III) Spiro Complexes: Synthesis, Structural Characterization, and Redox Transformation.有机铜（III）螺环配合物的合成、结构表征和氧化还原转化。
J Am Chem Soc. 2017 Oct 4;139(39):13688-13691. doi: 10.1021/jacs.7b08803. Epub 2017 Sep 25.
8
Partial Double Metal-Carbon Bonding Model in Transition Metal Methyl Compounds.过渡金属甲基化合物中的部分双金属-碳键模型。
Inorg Chem. 2022 Feb 14;61(6):2892-2902. doi: 10.1021/acs.inorgchem.1c03619. Epub 2022 Feb 1.
9
Organocopper(ii) complexes: new catalysts for carbon-carbon bond formation electrochemical atom transfer radical addition (ATRA).有机铜（II）配合物：用于碳-碳键形成的新型催化剂——电化学原子转移自由基加成（ATRA）。
Chem Sci. 2022 Aug 17;13(35):10506-10511. doi: 10.1039/d2sc03418b. eCollection 2022 Sep 14.
10
C(sp)-CF Reductive Elimination from a Five-Coordinate Neutral Copper(III) Complex.C(sp)-CF 还原消除反应：来自五配位中性铜(III)配合物的研究。
J Am Chem Soc. 2020 May 27;142(21):9785-9791. doi: 10.1021/jacs.0c03304. Epub 2020 May 18.
引用本文的文献
1
Oxidation States: Intrinsically Ambiguous?氧化态：本质上含混不清？
ACS Cent Sci. 2024 Jun 25;10(7):1406-1414. doi: 10.1021/acscentsci.4c00825. eCollection 2024 Jul 24.
2
Synergistic Charge Transfer Effect in Ferrous Heme-CO Bonding within Cytochrome P450.亚铁血红素-CO 键在细胞色素 P450 内的协同电荷转移效应。
Molecules. 2024 Feb 16;29(4):873. doi: 10.3390/molecules29040873.
3
Oxidative addition of an alkyl halide to form a stable Cu(III) product.卤代烷烃的氧化加成反应以形成稳定的Cu(III)产物。
Science. 2023 Sep 8;381(6662):1072-1079. doi: 10.1126/science.adg9232. Epub 2023 Sep 7.
4
Scrutinizing formally Ni centers through the lenses of core spectroscopy, molecular orbital theory, and valence bond theory.通过核心光谱学、分子轨道理论和价键理论的视角对镍中心进行形式上的审视。
Chem Sci. 2023 Jun 9;14(25):6915-6929. doi: 10.1039/d3sc02001k. eCollection 2023 Jun 28.
本文引用的文献
1
Combining Valence-to-Core X-ray Emission and Cu K-edge X-ray Absorption Spectroscopies to Experimentally Assess Oxidation State in Organometallic Cu(I)/(II)/(III) Complexes.结合价态到芯的 X 射线发射和 Cu K 边 X 射线吸收光谱实验评估有机金属 Cu(I)/(II)/(III) 配合物中的氧化态。
J Am Chem Soc. 2022 Feb 16;144(6):2520-2534. doi: 10.1021/jacs.1c09505. Epub 2022 Jan 20.
2
C(sp)-CF Reductive Elimination from a Five-Coordinate Neutral Copper(III) Complex.C(sp)-CF 还原消除反应：来自五配位中性铜(III)配合物的研究。
J Am Chem Soc. 2020 May 27;142(21):9785-9791. doi: 10.1021/jacs.0c03304. Epub 2020 May 18.
3
The Myth of d Copper(III).铜（III）的神话。
J Am Chem Soc. 2019 Nov 20;141(46):18508-18520. doi: 10.1021/jacs.9b09016. Epub 2019 Nov 11.
4
Charge-Shift Bonding: A New and Unique Form of Bonding.电荷转移键合：一种新型独特的键合形式。
Angew Chem Int Ed Engl. 2020 Jan 13;59(3):984-1001. doi: 10.1002/anie.201910085. Epub 2019 Nov 12.
5
σ-Noninnocence: Masked Phenyl-Cation Transfer at Formal Ni.σ-非无害性：形式上的镍处的掩蔽苯基阳离子转移
Angew Chem Int Ed Engl. 2019 Sep 9;58(37):13133-13139. doi: 10.1002/anie.201906658. Epub 2019 Jul 15.
6
A Key Intermediate in Copper-Mediated Arene Trifluoromethylation, [nBu N][Cu(Ar)(CF ) ]: Synthesis, Characterization, and C(sp )-CF Reductive Elimination.铜介导的芳烃三氟甲基化反应中的关键中间体，[正丁基铵][铜（芳基）（三氟甲基）]：合成、表征及C(sp²)-CF₃还原消除反应
Angew Chem Int Ed Engl. 2019 Jun 17;58(25):8510-8514. doi: 10.1002/anie.201904041. Epub 2019 May 13.
7
Csp-Csp Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes.Csp-Csp 键形成的由确定结构的铜（III）配合物引发的还原消除反应。
J Am Chem Soc. 2019 Feb 20;141(7):3153-3159. doi: 10.1021/jacs.8b12632. Epub 2019 Feb 6.
8
Experimental X-ray Electron Density Study of Atomic Charges, Oxidation States, and Inverted Ligand Field in Cu(CF).实验 X 射线电子密度研究原子电荷、氧化态和 Cu(CF)中的配体场反转。
Inorg Chem. 2019 Feb 4;58(3):2133-2139. doi: 10.1021/acs.inorgchem.8b03226. Epub 2019 Jan 15.
9
Spectroscopic Evidence for a 3d(10) Ground State Electronic Configuration and Ligand Field Inversion in [Cu(CF3)4](1-).光谱证据表明 [Cu(CF3)4](1-) 中存在 3d(10) 基态电子组态和配体场反转。
J Am Chem Soc. 2016 Feb 17;138(6):1922-31. doi: 10.1021/jacs.5b10819. Epub 2016 Feb 4.
10
Easy access to the copper(III) anion [Cu(CF3 )4 ](-).容易获得铜（III）阴离子 [Cu(CF3 )4 ](-)。
Angew Chem Int Ed Engl. 2015 Feb 23;54(9):2745-9. doi: 10.1002/anie.201411348. Epub 2015 Jan 21.
Zotero 插件