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

IF 1.5 4区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Helvetica Chimica Acta 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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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

Helvetica Chimica Acta 化学-化学综合

CiteScore

3.00

自引率

0.00%

发文量

审稿时长

2.3 months

期刊介绍： Helvetica Chimica Acta, founded by the Swiss Chemical Society in 1917, is a monthly multidisciplinary journal dedicated to the dissemination of knowledge in all disciplines of chemistry (organic, inorganic, physical, technical, theoretical and analytical chemistry) as well as research at the interface with other sciences, where molecular aspects are key to the findings. Helvetica Chimica Acta is committed to the publication of original, high quality papers at the frontier of scientific research. All contributions will be peer reviewed with the highest possible standards and published within 3 months of receipt, with no restriction on the length of the papers and in full color.