一个结构独特的{Fe(NO)2}10-{Fe(NO)2}9双核二硝基铁配合物，以μ-ƞ2-FBF3 -配体桥接，n -杂环卡宾稳定。

IF 3.7 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemistry - A European Journal Pub Date : 2025-09-17 DOI:10.1002/chem.202502404

Yung-Chuan Chuang, Ching-Wen Lin, Yi-Hung Wu, Yu-Hsien Chang, Chung-Hung Hsieh

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引用次数: 0

摘要

{Fe(NO)3}10三硝基铁配合物与单核{Fe(NO)2}10二硝基铁配合物反应得到双核二硝基铁配合物[(NO)2(IMes)Fe(μ-η -2- fbf3)Fe(IMes)(NO)2] (3) （IMes = 1,3-二（2,4,6-三甲基苯基）咪唑-2-酰基）。单晶x射线衍射揭示了一个前所未有的μ-η - 2- fbf3 -桥，连接两个[Fe(NO)2]基序，得到一个Fe....铁分离度3.45 Å。非经典的C─H…F接触（3.21 - 3.61 Å）之间的二甲酰基甲基和非桥接氟原子的阴离子，并创建一个伪三齿环境，稳定混合价核。红外光谱在1778、1736、1715和1682 cm-1处显示出四个ν(NO)波段，推断出两个电子不同的{Fe(NO)2}单元的存在，而77 K EPR光谱给出了一个gavg = 2.109的斜方波信号，诊断出配合物3中有一个s = 1/2的物质。

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A Structurally Unique {Fe(NO)₂}¹⁰-{Fe(NO)₂}⁹ Dinuclear Dinitrosyl Iron Complex Bridged by a μ-ƞ²-FBF₃ ^- Ligand and Stabilized by N-Heterocyclic Carbenes.

Reaction of a {Fe(NO)₃}¹⁰ trinitrosyl iron complex with a mononuclear {Fe(NO)₂}¹⁰ dinitrosyl iron complex furnishes a dinuclear dinitrosyl iron complex, [(NO)₂(IMes)Fe(μ-η²-FBF₃)Fe(IMes)(NO)₂] (3) (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene). Single-crystal X-ray diffraction reveals an unprecedented μ-η²-FBF₃ ^- bridge that links two [Fe(NO)₂] motifs, giving an Fe^….Fe separation of 3.45 Å. Nonclassical C─H^…F contacts (3.21 - 3.61 Å) between the mesityl methyl groups of the IMes and the nonbridging fluorine atom cradle the anion and create a pseudo-tridentate environment that stabilizes the mixed-valent core. Infrared spectroscopy exhibits four ν(NO) bands at 1778, 1736, 1715, and 1682 cm^-1, inferring the presence of two electronically different {Fe(NO)₂} units, whereas 77 K EPR spectroscopy gives a rhombic signal with g_avg = 2.109, diagnostic of an s = 1/2 species in complex 3.

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来源期刊

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.