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一整套铱（IV）吡啶醇盐立体异构体：高度依赖几何结构的氧化还原性质。

A full set of iridium(iv) pyridine-alkoxide stereoisomers: highly geometry-dependent redox properties.

作者信息

Shopov Dimitar Y, Rudshteyn Benjamin, Campos Jesús, Vinyard David J, Batista Victor S, Brudvig Gary W, Crabtree Robert H

机构信息

Department of Chemistry , Yale University , 225 Prospect St. , New Haven , CT 06520 , United States.

Energy Sciences Institute , Yale University , 520 West Campus Dr. , West Haven , CT 06516 , United States.

出版信息

Chem Sci. 2017 Feb 1;8(2):1642-1652. doi: 10.1039/c6sc03758e. Epub 2016 Nov 7.

DOI:10.1039/c6sc03758e
PMID:28451293
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5364517/
Abstract

We introduce and characterize the complete set of possible isomers of Ir(pyalk)Cl (pyalk = 2-(pyridin-2-yl)propan-2-oate), providing valuable insights on the properties of Ir(iv) species. The pyridine alkoxide ligand strongly stabilizes high oxidation states, essential to accessing the catalytically relevant Ir(iv) state, and results in robust complexes that can be handled under ambient conditions, even permitting chromatographic separation. The redox properties are isomer-dependent, spanning a 300 mV range, rationalized with ligand-field theory and DFT calculations. The reported complexes exhibit very high kinetic inertness against isomerization, despite highly disparate predicted thermodynamic stabilities, presenting a unique opportunity to study all five possible isomeric complexes with the same ligand set.

摘要

我们介绍并表征了Ir(pyalk)Cl（pyalk = 2-(吡啶-2-基)丙-2-醇盐）的全套可能异构体，为Ir(IV)物种的性质提供了有价值的见解。吡啶醇盐配体强烈稳定高氧化态，这对于获得催化相关的Ir(IV)态至关重要，并产生了可以在环境条件下处理的稳定配合物，甚至允许进行色谱分离。氧化还原性质取决于异构体，范围跨越300 mV，通过配体场理论和DFT计算进行了合理化解释。尽管预测的热力学稳定性差异很大，但所报道的配合物对异构化表现出非常高的动力学惰性，这为研究具有相同配体集的所有五种可能的异构配合物提供了独特的机会。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/41a4/5364517/c6403a9ffd22/c6sc03758e-f5.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/41a4/5364517/c6403a9ffd22/c6sc03758e-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/41a4/5364517/acc207a57bba/c6sc03758e-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/41a4/5364517/153275bbc793/c6sc03758e-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/41a4/5364517/d221188c322b/c6sc03758e-f1.jpg
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