由柔性14π三卟啉（2.1.1）和一种不寻常的Diels-Alder加合物衍生的双层二茂铁类似物：合成、表征和机理研究

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-03-28 DOI:10.1021/acs.inorgchem.5c0024910.1021/acs.inorgchem.5c00249

Ishfaq A. Bhat, Subhalaxmi Panda, Manju Sharma* and Pradeepta K. Panda*,

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引用次数: 0

摘要

14π-Triphyrin(2.1.1) 被用来合成类似二茂铁的双层夹心复合物。由于只存在两个介-CF3 取代基，大环具有足够的灵活性，可以发生碗状变形，从而与铁（II）离子复合，形成低自旋二磁性复合物。此外，金属载体[{Fe(CO)2(Cp)}2] 的 Cp 配体在较高温度下会与三氟乙烯大环形成 Diels-Alder 加合物，但不会发生络合反应。我们利用第一原理分子动力学探讨了[14]三聚吡啶(2.1.1)中形成夹心配合物背后的各种因素的可能作用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Double-Decker Ferrocene Analogue Derived from Flexible 14π Triphyrin(2.1.1) along with an Unusual Diels–Alder Adduct: Synthesis, Characterization, and Mechanistic Studies

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Double-Decker Ferrocene Analogue Derived from Flexible 14π Triphyrin(2.1.1) along with an Unusual Diels–Alder Adduct: Synthesis, Characterization, and Mechanistic Studies

14π-Triphyrin(2.1.1) is used to synthesize a double-decker sandwich complex like ferrocene. The presence of only two meso-CF₃ substituents provides the macrocycle with enough flexibility to undergo bowl-shaped deformation in order to complex with Fe(II) ions, forming a low-spin diamagnetic complex. Further, the Cp ligand of the metal carrier [{Fe(CO)₂(Cp)}₂] forms a Diels–Alder adduct with the triphyrin macrocycle at higher temperatures, which does not undergo complexation. The plausible role of factors behind the formation of sandwich complexes in [14]triphyrin(2.1.1) was explored using first-principles molecular dynamics.

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.