Facile Synthesis of an Octagermacubane with Two Three-Coordinate Germanium(0) Atoms and its Unique Radical Anion

Roman Bashkurov; Alexander Kaushansky; Boris Tumanskii; Natalia Fridman; Dmitry Bravo-Zhivotovskii; Yitzhak Apeloig

doi:10.1002/anie.202300847

Facile Synthesis of an Octagermacubane with Two Three-Coordinate Germanium(0) Atoms and its Unique Radical Anion

Roman Bashkurov, Alexander Kaushansky, Boris Tumanskii, Natalia Fridman, Dmitry Bravo-Zhivotovskii, Yitzhak Apeloig

Chemistry

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

1 Scopus citations

Abstract

Thermolysis of a 1 : 1 mixture of tris(di-tert-butylmethylsilyl)germane 9 and bis(di-tert-butylmethylsilyl)germane 17 at 100 °C produces unexpectedly octagermacubane 18, having two 3-coordinate Ge⁰ atoms (40 % yield). 18 was characterized by X-ray crystallography and it is a singlet biradical (according to DFT quantum mechanical calculations and the absence of an EPR signal). Reactions of 18 with CH₂Cl₂ and H₂O yield the novel dichloro-octagermacubane 24 and hydroxy-octagermacubane 25, respectively. Reduction of 18 with tBuMe₂SiNa in THF produces an isolable octagermacubane radical anion 26-Na. Based on X-ray crystallography, EPR spectroscopy and DFT quantum mechanical calculations, 26-Na is classified as a Ge-centered radical anion.

Original language	English
Article number	e202300847
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	18
DOIs	https://doi.org/10.1002/anie.202300847
State	Published - 24 Apr 2023

Keywords

Cluster Compounds
Cubanes
Germanium
Germylenes
Radical Anion

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.202300847

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title = "Facile Synthesis of an Octagermacubane with Two Three-Coordinate Germanium(0) Atoms and its Unique Radical Anion",

abstract = "Thermolysis of a 1 : 1 mixture of tris(di-tert-butylmethylsilyl)germane 9 and bis(di-tert-butylmethylsilyl)germane 17 at 100 °C produces unexpectedly octagermacubane 18, having two 3-coordinate Ge0 atoms (40 % yield). 18 was characterized by X-ray crystallography and it is a singlet biradical (according to DFT quantum mechanical calculations and the absence of an EPR signal). Reactions of 18 with CH2Cl2 and H2O yield the novel dichloro-octagermacubane 24 and hydroxy-octagermacubane 25, respectively. Reduction of 18 with tBuMe2SiNa in THF produces an isolable octagermacubane radical anion 26-Na. Based on X-ray crystallography, EPR spectroscopy and DFT quantum mechanical calculations, 26-Na is classified as a Ge-centered radical anion.",

keywords = "Cluster Compounds, Cubanes, Germanium, Germylenes, Radical Anion",

author = "Roman Bashkurov and Alexander Kaushansky and Boris Tumanskii and Natalia Fridman and Dmitry Bravo-Zhivotovskii and Yitzhak Apeloig",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

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AU - Bashkurov, Roman

AU - Kaushansky, Alexander

AU - Tumanskii, Boris

AU - Fridman, Natalia

AU - Bravo-Zhivotovskii, Dmitry

AU - Apeloig, Yitzhak

PY - 2023/4/24

Y1 - 2023/4/24

N2 - Thermolysis of a 1 : 1 mixture of tris(di-tert-butylmethylsilyl)germane 9 and bis(di-tert-butylmethylsilyl)germane 17 at 100 °C produces unexpectedly octagermacubane 18, having two 3-coordinate Ge0 atoms (40 % yield). 18 was characterized by X-ray crystallography and it is a singlet biradical (according to DFT quantum mechanical calculations and the absence of an EPR signal). Reactions of 18 with CH2Cl2 and H2O yield the novel dichloro-octagermacubane 24 and hydroxy-octagermacubane 25, respectively. Reduction of 18 with tBuMe2SiNa in THF produces an isolable octagermacubane radical anion 26-Na. Based on X-ray crystallography, EPR spectroscopy and DFT quantum mechanical calculations, 26-Na is classified as a Ge-centered radical anion.

AB - Thermolysis of a 1 : 1 mixture of tris(di-tert-butylmethylsilyl)germane 9 and bis(di-tert-butylmethylsilyl)germane 17 at 100 °C produces unexpectedly octagermacubane 18, having two 3-coordinate Ge0 atoms (40 % yield). 18 was characterized by X-ray crystallography and it is a singlet biradical (according to DFT quantum mechanical calculations and the absence of an EPR signal). Reactions of 18 with CH2Cl2 and H2O yield the novel dichloro-octagermacubane 24 and hydroxy-octagermacubane 25, respectively. Reduction of 18 with tBuMe2SiNa in THF produces an isolable octagermacubane radical anion 26-Na. Based on X-ray crystallography, EPR spectroscopy and DFT quantum mechanical calculations, 26-Na is classified as a Ge-centered radical anion.

KW - Cluster Compounds

KW - Cubanes

KW - Germanium

KW - Germylenes

KW - Radical Anion

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Facile Synthesis of an Octagermacubane with Two Three-Coordinate Germanium(0) Atoms and its Unique Radical Anion

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Keywords

ASJC Scopus subject areas

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