Speciation of Be2+in acidic liquid ammonia and formation of tetra- and octanuclear beryllium amido clusters

Matthias Müller; Antti J. Karttunen; Magnus R. Buchner

doi:10.1039/d0sc01112f

Speciation of Be²⁺in acidic liquid ammonia and formation of tetra- and octanuclear beryllium amido clusters

Matthias Müller, Antti J. Karttunen, Magnus R. Buchner^*

^*Corresponding author for this work

University of Marburg

Research output: Contribution to journal › Article › Scientific › peer-review

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Abstract

The hexa-μ₂-amido-tetraammine-tetraberyllium compounds [Be₄(NH₂)₆(NH₃)₄]X₂(X = Cl, Br, I, CN, SCN, N₃) have been prepared from beryllium metal and NH₄X or [Be(NH₃)₄]X₂in liquid ammonia at ambient temperature. The obtained compounds feature an adamantyl shaped complex cation, which was examinedviaX-ray diffraction, IR, Raman and NMR spectroscopy. The speciation in solution was studiedvia¹⁵N labeling experiments supplemented with quantum chemistry. Hereby, the intermediates [Be₂(NH₂)(NH₃)₆]³⁺and [Be₃(NH₂)₃(NH₃)₆]³⁺were identified. Reactivity studies provided bis(N-acetimidoylacetamidinato-N,N′)-beryllium(ii), when [Be₄(NH₂)₆(NH₃)₄]²⁺was treated with acetonitrile. While the unprecedented octa-nuclear complex cation [Be₈O(NH₂)₁₂(C₅H₅N)₄]²⁺was received from pyridine. This cluster proves that the [Be₄O]⁶⁺core can be stabilized without bidentateO-donor ligands.

Original language	English
Pages (from-to)	5415-5422
Number of pages	8
Journal	Chemical Science
Volume	11
Issue number	21
DOIs	https://doi.org/10.1039/d0sc01112f
Publication status	Published - 7 Jun 2020
MoE publication type	A1 Journal article-refereed

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@article{79f48a427f914997a6995fd77c98e030,

title = "Speciation of Be2+in acidic liquid ammonia and formation of tetra- and octanuclear beryllium amido clusters",

abstract = "The hexa-μ2-amido-tetraammine-tetraberyllium compounds [Be4(NH2)6(NH3)4]X2(X = Cl, Br, I, CN, SCN, N3) have been prepared from beryllium metal and NH4X or [Be(NH3)4]X2in liquid ammonia at ambient temperature. The obtained compounds feature an adamantyl shaped complex cation, which was examinedviaX-ray diffraction, IR, Raman and NMR spectroscopy. The speciation in solution was studiedvia15N labeling experiments supplemented with quantum chemistry. Hereby, the intermediates [Be2(NH2)(NH3)6]3+and [Be3(NH2)3(NH3)6]3+were identified. Reactivity studies provided bis(N-acetimidoylacetamidinato-N,N′)-beryllium(ii), when [Be4(NH2)6(NH3)4]2+was treated with acetonitrile. While the unprecedented octa-nuclear complex cation [Be8O(NH2)12(C5H5N)4]2+was received from pyridine. This cluster proves that the [Be4O]6+core can be stabilized without bidentateO-donor ligands.",

author = "Matthias M{\"u}ller and Karttunen, {Antti J.} and Buchner, {Magnus R.}",

year = "2020",

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doi = "10.1039/d0sc01112f",

language = "English",

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journal = "Chemical Science",

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TY - JOUR

T1 - Speciation of Be2+in acidic liquid ammonia and formation of tetra- and octanuclear beryllium amido clusters

AU - Müller, Matthias

AU - Karttunen, Antti J.

AU - Buchner, Magnus R.

PY - 2020/6/7

Y1 - 2020/6/7

N2 - The hexa-μ2-amido-tetraammine-tetraberyllium compounds [Be4(NH2)6(NH3)4]X2(X = Cl, Br, I, CN, SCN, N3) have been prepared from beryllium metal and NH4X or [Be(NH3)4]X2in liquid ammonia at ambient temperature. The obtained compounds feature an adamantyl shaped complex cation, which was examinedviaX-ray diffraction, IR, Raman and NMR spectroscopy. The speciation in solution was studiedvia15N labeling experiments supplemented with quantum chemistry. Hereby, the intermediates [Be2(NH2)(NH3)6]3+and [Be3(NH2)3(NH3)6]3+were identified. Reactivity studies provided bis(N-acetimidoylacetamidinato-N,N′)-beryllium(ii), when [Be4(NH2)6(NH3)4]2+was treated with acetonitrile. While the unprecedented octa-nuclear complex cation [Be8O(NH2)12(C5H5N)4]2+was received from pyridine. This cluster proves that the [Be4O]6+core can be stabilized without bidentateO-donor ligands.

AB - The hexa-μ2-amido-tetraammine-tetraberyllium compounds [Be4(NH2)6(NH3)4]X2(X = Cl, Br, I, CN, SCN, N3) have been prepared from beryllium metal and NH4X or [Be(NH3)4]X2in liquid ammonia at ambient temperature. The obtained compounds feature an adamantyl shaped complex cation, which was examinedviaX-ray diffraction, IR, Raman and NMR spectroscopy. The speciation in solution was studiedvia15N labeling experiments supplemented with quantum chemistry. Hereby, the intermediates [Be2(NH2)(NH3)6]3+and [Be3(NH2)3(NH3)6]3+were identified. Reactivity studies provided bis(N-acetimidoylacetamidinato-N,N′)-beryllium(ii), when [Be4(NH2)6(NH3)4]2+was treated with acetonitrile. While the unprecedented octa-nuclear complex cation [Be8O(NH2)12(C5H5N)4]2+was received from pyridine. This cluster proves that the [Be4O]6+core can be stabilized without bidentateO-donor ligands.

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U2 - 10.1039/d0sc01112f

DO - 10.1039/d0sc01112f

M3 - Article

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SN - 2041-6520

VL - 11

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EP - 5422

JO - Chemical Science

JF - Chemical Science

IS - 21

ER -

Speciation of Be²⁺in acidic liquid ammonia and formation of tetra- and octanuclear beryllium amido clusters

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