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

Funding

M. R. B. thanks Prof. F. Kraus for moral and financial support as well as the provision of laboratory space. The DFG is gratefully acknowledged for financial support (BU2725/5-1 & BU2725/8-1). A. J. K thanks CSC - the Finnish IT Center for Science for computational resources.

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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",

volume = "11",

pages = "5415--5422",

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.

UR - https://www.scopus.com/pages/publications/85085984995

U2 - 10.1039/d0sc01112f

DO - 10.1039/d0sc01112f

M3 - Article

AN - SCOPUS:85085984995

SN - 2041-6520

VL - 11

SP - 5415

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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