κ²-N,N'-Sulfurdiimide and κ¹-O-Sulfinylamine Complexes of Tin(IV) Chloride.

IF 3.7 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemistry - A European Journal Pub Date : 2025-09-25 DOI:10.1002/chem.202502342

Nathan D D Hill, René T Boeré

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引用次数: 0

Abstract

A series of Sn(IV) chloride complexes with sulfur diimide (SDI, R-NSN-R) ligands are presented, including structural characterization of first-in-class complexes of bidentate diaryl-SDIs, [SnCl₄{κ²-N,N'-S(NAr)₂}] (Ar = 4-X-C₆H₄-), and an oxygen-coordinated sulfinylamine, [SnCl₄{κ¹-O-OSNPh}₂]. As part of the comprehensive experimental and DFT computational investigation, ¹¹⁹Sn NMR analysis revealed a dynamic exchange equilibrium in acetonitrile between SDI ligands and solvent, providing insight into their complicated solution-state chemical and electrochemical behavior. Voltammetric experiments show that, despite this dynamic equilibrium, the SDI ligands appear to suppress typical Sn(IV) reduction pathways. While tentative due to the complex behavior, this suggests that SDIs are functioning as redox-active (RA) ligands. In conjunction with our previous systematic characterization of diaryl-SDIs, these findings highlight their potential as an easily derivatized and highly redox-tunable category of RA ligand and emphatically warrant further investigation.

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氯化锡的κ2-N，N'-硫酰亚胺和κ1- o -亚胺配合物。

介绍了一系列含硫二亚胺（SDI, R-NSN-R）的Sn（IV）氯配合物，包括双齿二芳基SDI配合物[SnCl4{κ2-N，N'- s (NAr)2}] （Ar = 4-X-C6H4-）和氧配位亚胺[SnCl4{κ1-O-OSNPh}2]的结构表征。作为综合实验和DFT计算研究的一部分，119Sn核磁共振分析揭示了SDI配体与溶剂在乙腈中的动态交换平衡，为其复杂的溶液态化学和电化学行为提供了见解。伏安实验表明，尽管存在这种动态平衡，SDI配体似乎抑制了典型的Sn（IV）还原途径。由于其复杂的行为，这表明sdi具有氧化还原活性（RA）配体的功能。结合我们之前对二芳基sdi的系统表征，这些发现突出了它们作为一种易于衍生和高度氧化还原可调的RA配体的潜力，并强调值得进一步研究。

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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.