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异金属分子异构体和离子异构体。

Heterometallic Molecular and Ionic Isomers.

作者信息

Zhang Yuxuan, Wei Zheng, Han Haixiang, Chang Joyce, Stegman Samantha, Chang Tieyan, Chen Yu-Sheng, Berry John F, Dikarev Evgeny V

机构信息

Department of Chemistry, University at Albany, Albany, New York 12222, United States.

School of Materials Science and Engineering, Tongji University, Shanghai 201804, China.

出版信息

Inorg Chem. 2024 Oct 14;63(41):19499-19508. doi: 10.1021/acs.inorgchem.4c03849. Epub 2024 Oct 3.

DOI:10.1021/acs.inorgchem.4c03849
PMID:39363602
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11483736/
Abstract

Numerous descriptions of structural isomerism in metal complexes do not list any molecular vs ionic isomers. At the same time, one of the most striking examples of structural isomerism in organic chemistry is molecular urea, which has the same atomic composition as the chemically distinct ionic ammonium cyanate. This iconic organic couple now meets its inorganic heterometallic counterpart. We introduce a new class of structural isomers, molecular vs ionic, that can be consummated in complex and coordinatively unsaturated polynuclear/heterometallic compounds. We report inorganic molecular and ionic isomers of the composition [NaCrFe (acac)(hfac)] (acac = acetylacetonate; hfac = hexafluoroacetylacetonate). Heterometallic molecular [Cr(acac)-Na-Fe(hfac)] () and ionic {[Cr(acac)-Na-Cr(acac)][Fe(hfac)-Na-Fe(hfac)]} () isomers have been isolated in pure form and characterized. While both ions are heterometallic trinuclear entities, the neutral counterpart is a heterometallic trinuclear molecule. The two isomers exhibit distinctly different characteristics in terms of solubility, volatility, mass spectrometry ionization, and thermal behavior. Unambiguous assignment of the positions and oxidation/spin states of the Periodic Table neighbors, Fe and Cr, in both isomers have been made by a combination of characterization techniques that include synchrotron X-ray resonant diffraction, synchrotron X-ray fluorescence spectroscopy, Mössbauer spectroscopy, and DART mass spectrometry. The transformation between the two isomers that does take place in solutions of noncoordinating solvents has also been tested.

摘要

金属配合物中结构异构的众多描述并未列出任何分子异构体与离子异构体。与此同时，有机化学中结构异构最显著的例子之一是分子尿素，它与化学性质不同的离子型氰酸铵具有相同的原子组成。这一标志性的有机组合现在有了其无机异金属对应物。我们引入了一类新的结构异构体，即分子异构体与离子异构体，它们可以在复杂且配位不饱和的多核/异金属化合物中实现。我们报道了组成为[NaCrFe(acac)(hfac)]（acac = 乙酰丙酮；hfac = 六氟乙酰丙酮）的无机分子异构体和离子异构体。已分离出纯形式的异金属分子[Cr(acac)-Na-Fe(hfac)]（）和离子型{[Cr(acac)-Na-Cr(acac)][Fe(hfac)-Na-Fe(hfac)]}（）异构体并对其进行了表征。虽然这两种离子都是异金属三核实体，但中性对应物是一个异金属三核分子。这两种异构体在溶解性、挥发性、质谱电离和热行为方面表现出明显不同的特征。通过包括同步加速器X射线共振衍射、同步加速器X射线荧光光谱、穆斯堡尔光谱和DART质谱在内的多种表征技术组合，明确确定了两种异构体中元素周期表相邻元素Fe和Cr的位置以及氧化态/自旋态。还测试了在非配位溶剂溶液中确实会发生的两种异构体之间的转化。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b233/11483736/461b03c9c4b5/ic4c03849_0010.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b233/11483736/c744c2788951/ic4c03849_0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b233/11483736/1a3ba28dba51/ic4c03849_0012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b233/11483736/540554d0e797/ic4c03849_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b233/11483736/f84a872e3f07/ic4c03849_0002.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b233/11483736/135b9d8a6150/ic4c03849_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b233/11483736/7a54dfa0b487/ic4c03849_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b233/11483736/d611f9daafd2/ic4c03849_0007.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b233/11483736/461b03c9c4b5/ic4c03849_0010.jpg

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