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具有非惰性氰基配体的高铁（-IV）酸盐和钌（-IV）酸盐。

Tricyanidoferrates(-IV) and Ruthenates(-IV) with Non-Innocent Cyanido Ligands.

作者信息

Jach Franziska, Wagner Frank R, Amber Zeeshan H, Rüsing Michael, Hunger Jens, Prots Yurii, Kaiser Martin, Bobnar Matej, Jesche Anton, Eng Lukas M, Ruck Michael, Höhn Peter

机构信息

Max-Planck-Institute for Chemical Physics of Solids, Nöthnitzer Strasse 40, 01187, Dresden, Germany.

Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062, Dresden, Germany.

出版信息

Angew Chem Int Ed Engl. 2021 Jul 12;60(29):15879-15885. doi: 10.1002/anie.202103268. Epub 2021 Jun 15.

DOI:10.1002/anie.202103268
PMID:33938602
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8362014/
Abstract

Exceptionally electron-rich, nearly trigonal-planar tricyanidometalate anions [Fe(CN) ] and [Ru(CN) ] were stabilized in LiSr [Fe(CN) ] and AE [M(CN) ] (AE=Sr, Ba; M=Fe, Ru). They are the first examples of group 8 elements with the oxidation state of -IV. Microcrystalline powders were obtained by a solid-state route, single crystals from alkali metal flux. While LiSr [Fe(CN) ] crystallizes in P6 /m, the polar space group P6 with three-fold cell volume for AE [M(CN) ] is confirmed by second harmonic generation. X-ray diffraction, IR and Raman spectroscopy reveal longer C-N distances (124-128 pm) and much lower stretching frequencies (1484-1634 cm ) than in classical cyanidometalates. Weak C-N bonds in combination with strong M-C π-bonding is a scheme also known for carbonylmetalates. Instead of the formal notation [Fe (CN ) ] , quantum chemical calculations reveal non-innocent intermediate-valent CN ligands and a closed-shell d configuration for Fe, that is, Fe .

摘要

电子云密度极高、近乎三角平面的三氰基金属酸根阴离子[Fe(CN)₆]⁴⁻和[Ru(CN)₆]⁴⁻在LiSr₂[Fe(CN)₆]和AE₂[M(CN)₆]（AE = Sr、Ba；M = Fe、Ru）中得以稳定存在。它们是氧化态为-IV的第8族元素的首例。微晶粉末通过固相法制备，单晶则由碱金属助熔剂法得到。虽然LiSr₂[Fe(CN)₆]以P6/m空间群结晶，但通过二次谐波产生证实了具有三倍晶胞体积的极性空间群P6的AE₂[M(CN)₆]。X射线衍射、红外和拉曼光谱显示，与经典的氰基金属酸盐相比，其C-N键长更长（124 - 128 pm），伸缩频率更低（1484 - 1634 cm⁻¹）。弱的C-N键与强的M-C π键相结合，这也是羰基金属酸盐所熟知的一种结构。量子化学计算表明，并非形式上的[Fe(Ⅱ)(CN)₆]⁴⁻，而是存在非单纯的中间价态CN配体以及Fe的闭壳层d⁶构型，即Fe(Ⅱ)。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/05d9/8362014/de7122f29bf0/ANIE-60-15879-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/05d9/8362014/e511e3d4f91e/ANIE-60-15879-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/05d9/8362014/a8674f26d265/ANIE-60-15879-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/05d9/8362014/9cde4c7bf144/ANIE-60-15879-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/05d9/8362014/de7122f29bf0/ANIE-60-15879-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/05d9/8362014/e511e3d4f91e/ANIE-60-15879-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/05d9/8362014/a8674f26d265/ANIE-60-15879-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/05d9/8362014/9cde4c7bf144/ANIE-60-15879-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/05d9/8362014/de7122f29bf0/ANIE-60-15879-g001.jpg

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