Synthesis and Reactivity of a Non-Heme μ-Oxodicobalt(IV) Complex

IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Simarjeet Kaur, Kritika Keshari, Maxime Sauvan, Lucia Velasco, Pragya Arora, Aakash Santra, Asterios Charisiadis, Ashok D. Ugale, Apparao Draksharapu, Dooshaye Moonshiram, Sayantan Paria
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Abstract

A mononuclear CoIII complex (1) of a bisamide-bisalkoxide donor ligand was synthesized and thoroughly characterized. The reaction of 1 with 0.5 equiv. of m-chloroperbenzoic acid (m-CPBA) in acetonitrile at −40 °C resulted in the formation of a μ-oxodicobalt(IV) complex (2), which was characterized by an array of spectroscopic techniques, including X-ray absorption spectroscopy which revealed a short Co−Ooxo distance of 1.67 Å. Reactivity studies of 2 towards oxidation/oxygenation of hydrocarbon C−H bond and triphenylphosphine or thioanisole derivatives have been examined. UV-vis spectroscopy studies showed the appearance of clear isosbestic points during the oxidation of substrates together with a neat transformation of 2 to 1. Detailed kinetic investigations established that 2 follows a Concerted Proton-Electron Transfer (CPET) mechanism for hydrocarbon oxidation and has a weak electrophilic character. Catalytic behavior of 1 was noted towards the oxygen atom transfer reactions. This study showcases the spectroscopic investigation and reactivity studies of a CoIV(μ-O)CoIV moiety. Although the FeIV analog of such a core has been described before, the study describes the first example with a CoIV center.

Abstract Image

非血红素μ-氧二钴(IV)配合物的合成及反应性。
合成了一种双酰胺-双醇酸给体的单核CoIII配合物(1),并对其进行了表征。1与0.5等量的间氯过苯甲酸(m-CPBA)在乙腈中在-40℃下反应生成μ-氧二钴(IV)配合物(2),通过一系列光谱技术对其进行了表征,包括x射线吸收光谱,发现其Co-Ooxo距离为1.67 Å。研究了2对碳氢化合物C-H键和三苯基膦或硫代苯甲醚衍生物的氧化/氧化反应性。紫外-可见光谱研究表明,在底物氧化过程中出现了清晰的等吸点,并伴有2到1的整齐转变。详细的动力学研究表明,2遵循协调质子-电子转移(CPET)机制进行碳氢化合物氧化,具有弱亲电性。注意到1对氧原子转移反应的催化行为。本研究展示了一个CoIV(μ-O)CoIV片段的光谱研究和反应性研究。虽然以前已经描述过这种核心的FeIV模拟物,但该研究描述了第一个具有CoIV中心的例子。
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来源期刊
Chemistry - A European Journal
Chemistry - A European Journal 化学-化学综合
CiteScore
7.90
自引率
4.70%
发文量
1808
审稿时长
1.8 months
期刊介绍: Chemistry—A European Journal is a truly international journal with top quality contributions (2018 ISI Impact Factor: 5.16). It publishes a wide range of outstanding Reviews, Minireviews, Concepts, Full Papers, and Communications from all areas of chemistry and related fields. Based in Europe Chemistry—A European Journal provides an excellent platform for increasing the visibility of European chemistry as well as for featuring the best research from authors from around the world. All manuscripts are peer-reviewed, and electronic processing ensures accurate reproduction of text and data, plus short publication times. The Concepts section provides nonspecialist readers with a useful conceptual guide to unfamiliar areas and experts with new angles on familiar problems. Chemistry—A European Journal is published on behalf of ChemPubSoc Europe, a group of 16 national chemical societies from within Europe, and supported by the Asian Chemical Editorial Societies. The ChemPubSoc Europe family comprises: Angewandte Chemie, Chemistry—A European Journal, European Journal of Organic Chemistry, European Journal of Inorganic Chemistry, ChemPhysChem, ChemBioChem, ChemMedChem, ChemCatChem, ChemSusChem, ChemPlusChem, ChemElectroChem, and ChemistryOpen.
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