Fluorinated-Thiolate Osmium(III) and Osmium(IV) Complexes Bearing N,N-diethyldithiocarbamate and Substituted Phosphines. Synthesis, Crystal Structures and DFT-Studies

IF 16.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Accounts of Chemical Research Pub Date : 2024-07-05 DOI:10.1002/hlca.202400066

Bertín Anzaldo, Andrés Álvarez-García, Sylvain Bernès, Armando Ramírez-Monroy, Maribel Arroyo-Carranza

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引用次数: 0

Abstract

The paramagnetic osmium(III) [Os(SR_F)(S₂CNEt₂)₂(P(C₆H₄X-4)₃)] (R_F=C₆F₄H−4, C₆F₅; X=OCH₃, CH₃, F) (1–6) along with diamagnetic osmium(IV) [Os(SR_F)₂(S₂CNEt₂)₂] (7–8) complexes were obtained from [Os(SR_F)₄(P(C₆H₄-X)₃)] and NaS₂CNEt₂, which were characterized by FAB mass spectrometry, IR spectroscopy, single crystal X-ray diffraction, and for the diamagnetic 7 also by NMR. TD-DFT calculations were performed to simulate the absorption spectra of complexes. In the visible region, LMCT transitions contribute to the calculated intensities, which are somewhat related to the color of the synthesized compounds. In the ultraviolet region, the phosphine ligand plays a significant role in MLCT transitions, which results in Os(III) complexes exhibiting an intense band in that region. Topological analysis and electron localization function (ELF) maps calculated for 6 and 7 confirm the strong ionic character of the Os−S coordination bonds formed by the thiophenolate and dithiocarbamate ligands. This comprehensive study provides information on the structure, bonding, and electronic properties of osmium complexes, for potential applications in catalysis, materials science, and biological systems.

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含 N,N-二乙基二硫代氨基甲酸酯和取代膦的氟硫酸盐锇(III)和锇(IV)配合物：合成、晶体结构和 DFT 研究

顺磁性锇（III）[Os(SRF)(S2CNEt2)2(P(C6H4X-4)3)]（RF = C6F4H-4，C6F5；从 [Os(SRF)4(P(C6H4-X)3)] 和 NaS2CNEt2 中得到了[Os(SRF)4(P(C6H4-X)3)](1-6) 以及二磁性锇（IV）[Os(SRF)2(S2CNEt2)2](7-8) 复合物，并通过 FAB 质谱法、红外光谱法、单晶 X 射线衍射法以及核磁共振法对二磁性 7 进行了表征。为模拟复合物的吸收光谱，进行了 TD-DFT 计算。在可见光区域，LMCT 转变有助于计算强度，这与合成化合物的颜色有一定关系。在紫外区，膦配体在 MLCT 转变中发挥了重要作用，这使得 Os(III) 复合物在该区域显示出一个强带。为 6 和 7 计算的拓扑分析和电子定位功能图证实，噻吩酚配体和二硫代氨基甲酸酯配体形成的 Os-S 配位键具有很强的离子特性。这项综合研究提供了有关锇配合物的结构、成键和电子特性的信息，具有在催化、材料科学和生物系统中应用的潜力。

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来源期刊

Accounts of Chemical Research 化学-化学综合

CiteScore

31.40

自引率

1.10%

发文量

312

审稿时长

2 months

期刊介绍： Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.