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首页> 外文期刊>Organometallics >C-2-Symmetric Hindered 'Sandwich' Chiral N-Heterocyclic Carbene Precursors and Their Transition Metal Complexes: Expedient Syntheses, Structural Authentication, and Catalytic Properties
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C-2-Symmetric Hindered 'Sandwich' Chiral N-Heterocyclic Carbene Precursors and Their Transition Metal Complexes: Expedient Syntheses, Structural Authentication, and Catalytic Properties

机译：C-2 - 对称阻碍“夹心”手性N-杂环卡链前体及其过渡金属配合物：有利合成，结构认证和催化性质

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摘要

We present here a new family of C-2-symmetric "sandwich" NHC ligands abbreviated as SITLAr and BzITL(Ar) and their complexes. The chiral fragments incorporate bulky yet flexible cyclohexyl groups with alpha-stereocenters joined to nitrogens individually, which set up chiral pockets around pivotal carbene carbons (less than 2.5 angstrom). Full characterization revealed unique structures with roughly parallel aryl moieties above and below imidazoline and benzimidazole planes in the Z-shaped arrangement. Extra hydrogen bonding interactions and steric stress between the square-planar frameworks and aryl groups led to the exceptional confinement and reversed the configurations in the iridium complexes. In accordance with Tolman's electronic parameters and topographic steric maps of well-established metalated complexes, these new ligands possess strong electron-donating properties and exceptionally steric demands. Additionally, the preliminary results employing the BzITL(Ar) ligands allowed appropriate activities and provided potential applications for asymmetric induction in the enantioselective aryl transfer and hydrosilylation reactions with moderate enantioselectivity.
机译：我们在座的一个新系列C-2-对称的“三明治” NHC配位体，简称SITLAr和BzITL（Ar）和它们的复合物。手性片段结合笨重而又灵活的环己基基团与连接到氮单独的α-立体中心，其周围设置了枢轴卡宾碳原子的手性口袋（大于2.5埃以下）。充分表征揭示独特结构与上面和下面的咪唑啉和苯并咪唑在Z形布置的平面大致平行的芳基部分。额外的氢键相互作用，并导致优异的约束的正方形平面框架和芳基之间的空间位应力和扭转的铱络合物的结构。根据托尔曼的电子参数和完善化络合物的地形图空间，这些新的配体具有较强的电子性质和异常空间的需求。此外，采用BzITL（Ar）的初步结果配位体允许适当的活动并在适度的对映选择性的对映选择性芳转移和氢化硅烷化反应提供了一种用于不对称诱导的潜在应用。

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  • 来源
    《Organometallics》 |2018年第21期|共14页
  • 作者

    Liu Cong; Shen Hong-Qiang; Chen Mu-Wang; Zhou Yong-Gui;

  • 作者单位

    Chinese Acad Sci Dalian Inst Chem Phys State Key Lab Catalysis Dalian 116023 Peoples R China;

    Chinese Acad Sci Dalian Inst Chem Phys State Key Lab Catalysis Dalian 116023 Peoples R China;

    Chinese Acad Sci Dalian Inst Chem Phys State Key Lab Catalysis Dalian 116023 Peoples R China;

    Chinese Acad Sci Dalian Inst Chem Phys State Key Lab Catalysis Dalian 116023 Peoples R China;

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  • 正文语种 eng
  • 中图分类 元素有机化合物;
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