Synthesis of Quinoline-Based Pt–Sb Complexes with L- or Z-Type Interaction: Ligand-Controlled Redox via Anion Transfer

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2024-08-13 DOI:10.1021/acs.organomet.4c0022110.1021/acs.organomet.4c00221

Christopher K. Webber, Fanji Kong, Jugal Kumawat, Jyothish Joy, Erica K. Richardson, Paolo Siano, Diane A. Dickie, Daniel H. Ess* and T. Brent Gunnoe*,

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Abstract

A series of Pt–Sb complexes with two or three L-type quinoline side arms were prepared and studied. Two ligands, tri(8-quinolinyl)stibane (SbQ₃, Q = 8-quinolinyl, 1) and 8,8′-(phenylstibanediyl)diquinoline (SbQ₂Ph, 2), were used to synthesize the Pt^II–Sb^III complexes (SbQ₃)PtCl₂ (3) and (SbQ₂Ph)PtCl₂ (4). Chloride abstraction with AgOAc provided the bis-acetate complexes (SbQ₃)Pt(OAc)₂ (5) and (SbQ₂Ph)Pt(OAc)₂ (6). To better understand the electronic effects of the Sb moiety, analogous bis-chloride complexes were oxidized to an overall formal oxidation state of +7 (i.e., Pt + Sb formal oxidation states = 7) using dichloro(phenyl)-λ³-iodane (PhICl₂) and 3,4,5,6-tetrachloro-1,2-dibenzoquinone (o-chloranil) as two-electron oxidants. Depending on the oxidant, different conformational changes occur within the coordination sphere of Pt as confirmed by single-crystal X-ray diffraction and NMR spectroscopy. In addition, the nature of Pt–Sb interactions was evaluated via molecular and localized orbital calculations.

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具有 L 型或 Z 型相互作用的喹啉基 Pt-Sb 配合物的合成：通过阴离子转移实现配体控制氧化还原

我们制备并研究了一系列具有两个或三个 L 型喹啉侧臂的铂锑配合物。研究人员使用两种配体，即三(8-喹啉基)锡烷（SbQ3，Q = 8-喹啉基，1）和 8,8′-(苯基锡烷二基)二喹啉（SbQ2Ph，2），合成了 PtII-SbIII 配合物 (SbQ3)PtCl2 (3) 和 (SbQ2Ph)PtCl2 (4)。用 AgOAc 萃取氯化物可得到双乙酸酯配合物 (SbQ3)Pt(OAc)2 (5) 和 (SbQ2Ph)Pt(OAc)2 (6)。为了更好地理解 Sb 分子的电子效应，我们使用二氯（苯基）-λ3-碘烷（PhICl2）和 3,4,5,6-四氯-1,2-二苯醌（邻氯苯醌）作为双电子氧化剂，将类似的双氯化物配合物氧化至总的形式氧化态为 +7（即 Pt + Sb 形式氧化态 = 7）。单晶 X 射线衍射和核磁共振光谱证实，根据氧化剂的不同，铂的配位层会发生不同的构象变化。此外，还通过分子和局部轨道计算评估了铂锑相互作用的性质。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.