Decreasing the Bond Order between Vanadium and Oxo Ligand to Form 3d Schrock Carbynes

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Journal of the American Chemical Society Pub Date : 2024-07-05 DOI:10.1021/jacs.4c07588
Shirley Hernandez, Dmitry S. Belov, Vasilisa Krivovicheva, Shuruthi Senthil and Konstantin V. Bukhryakov*, 
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Abstract

Preserving vanadium in a high oxidation state during chemical transformations can be challenging due to the oxidizing nature of V(+5) species. Oxo and similar isoelectronic ligands have been utilized to stabilize V(+5) by extensive π-donation. However, decreasing the bond order between V and the oxo ligand often results in a reduction of the metal center. Herein, we report a unique transformation involving anionic V(+5) alkylidene that converts a V(+5) oxo complex to a V(+5) alkylidyne in three steps without altering the oxidation state of the metal center. This method has been used to obtain rare 3d Schrock carbynes, which provide easy and scalable access to V(+5) alkylidynes.

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降低钒与氧化配体之间的键序以形成 3d Schrock 碳炔。
由于 V(+5)具有氧化性,因此在化学转化过程中保持钒的高氧化态具有挑战性。人们利用氧化配体和类似的等电子配体通过广泛的π-捐赠来稳定 V(+5)。然而,降低 V 与氧化配体之间的键序往往会导致金属中心的降低。在此,我们报告了一种涉及阴离子 V(+5)亚烷基的独特转化方法,它能在不改变金属中心氧化态的情况下,通过三个步骤将 V(+5)氧代配合物转化为 V(+5)亚烷基。这种方法已被用于获得稀有的 3d Schrock 碳炔,为获得 V(+5)亚烷基提供了简便、可扩展的途径。
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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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