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具有L型或Z型相互作用的喹啉基铂-锑配合物的合成：通过阴离子转移实现配体控制的氧化还原反应

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

作者信息

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

机构信息

Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, United States.

Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84604, United States.

出版信息

Organometallics. 2024 Aug 13;43(17):1789-1802. doi: 10.1021/acs.organomet.4c00221. eCollection 2024 Sep 9.

DOI:10.1021/acs.organomet.4c00221
PMID:39268180
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11388469/
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 (SbQ, Q = 8-quinolinyl, ) and 8,8'-(phenylstibanediyl)diquinoline (SbQPh, ), were used to synthesize the Pt-Sb complexes (SbQ)PtCl () and (SbQPh)PtCl (). Chloride abstraction with AgOAc provided the bis-acetate complexes (SbQ)Pt(OAc) () and (SbQPh)Pt(OAc) (). 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)-λ-iodane (PhICl) and 3,4,5,6-tetrachloro-1,2-dibenzoquinone (-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.

摘要

制备并研究了一系列带有两个或三个L型喹啉侧臂的铂 - 锑配合物。使用两种配体，三（8 - 喹啉基）锑烷（SbQ，Q = 8 - 喹啉基）和8,8' - （苯基二锑基）二喹啉（SbQPh）来合成铂 - 锑配合物（SbQ）PtCl（）和（SbQPh）PtCl（）。用醋酸银进行氯取代得到双醋酸盐配合物（SbQ）Pt（OAc）（）和（SbQPh）Pt（OAc）（）。为了更好地理解锑部分的电子效应，使用二氯（苯基） - λ - 碘烷（PhICl）和3,4,5,6 - 四氯 - 1,2 - 二苯醌（ - 四氯苯醌）作为双电子氧化剂，将类似的双氯化物配合物氧化至总形式氧化态为 +7（即铂 + 锑的形式氧化态 = 7）。根据氧化剂的不同，单晶X射线衍射和核磁共振光谱证实，铂的配位球内会发生不同的构象变化。此外，通过分子和定域轨道计算评估了铂 - 锑相互作用的性质。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5541/11388469/a1afa92adf95/om4c00221_0008.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5541/11388469/70aaba0475c9/om4c00221_0005.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5541/11388469/a1afa92adf95/om4c00221_0008.jpg

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