Tetrakis(di-tert-butylmethylsilyl)digermene: Synthesis, structure, electrochemical properties, and reactivity

Vladimir Ya Lee; Kiera McNiece; Yuki Ito; Akira Sekiguchi; Natalie Geinik; James Y. Becker

doi:10.1002/hc.21165

Tetrakis(di-tert-butylmethylsilyl)digermene: Synthesis, structure, electrochemical properties, and reactivity

Vladimir Ya Lee, Kiera McNiece, Yuki Ito, Akira Sekiguchi, Natalie Geinik, James Y. Becker

Department of Chemistry

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

19 Scopus citations

Abstract

The tetrasilyl-substituted digermene (^tBu₂MeSi)₂Ge=Ge(SiMe^tBu₂)₂ 1 was prepared by the reduction of the readily available 1,1-dichlorogermane (^tBu₂MeSi)₂GeCl₂ with potassium graphite. Compound 1 is a rather unusual example of a digermene featuring planar geometry at the doubly bonded germanium atoms, on the one hand, and an extraordinarily twisted Ge=Ge bond, on the other hand, caused by the electronic and steric factors of the bulky σ-donating silyl substituents. Although it maintains the structural integrity of its double bond in solution, 1 revealed reactivity that is not characteristic of the >Ge=Ge< bond but is typical for germylenes >Ge: upon reaction with nucleophilic reagents (isocyanide, orthoquinone). Unlike common alkenes, 1 affords stable cation and anion radicals generated by cyclic voltammetry.

Original language	English
Pages (from-to)	313-319
Number of pages	7
Journal	Heteroatom Chemistry
Volume	25
Issue number	5
DOIs	https://doi.org/10.1002/hc.21165
State	Published - 1 Nov 2014

ASJC Scopus subject areas

General Chemistry

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title = "Tetrakis(di-tert-butylmethylsilyl)digermene: Synthesis, structure, electrochemical properties, and reactivity",

abstract = "The tetrasilyl-substituted digermene (tBu2MeSi)2Ge=Ge(SiMetBu2)2 1 was prepared by the reduction of the readily available 1,1-dichlorogermane (tBu2MeSi)2GeCl2 with potassium graphite. Compound 1 is a rather unusual example of a digermene featuring planar geometry at the doubly bonded germanium atoms, on the one hand, and an extraordinarily twisted Ge=Ge bond, on the other hand, caused by the electronic and steric factors of the bulky σ-donating silyl substituents. Although it maintains the structural integrity of its double bond in solution, 1 revealed reactivity that is not characteristic of the >Ge=Ge< bond but is typical for germylenes >Ge: upon reaction with nucleophilic reagents (isocyanide, orthoquinone). Unlike common alkenes, 1 affords stable cation and anion radicals generated by cyclic voltammetry.",

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T2 - Synthesis, structure, electrochemical properties, and reactivity

AU - Lee, Vladimir Ya

AU - McNiece, Kiera

AU - Ito, Yuki

AU - Sekiguchi, Akira

AU - Geinik, Natalie

AU - Becker, James Y.

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AB - The tetrasilyl-substituted digermene (tBu2MeSi)2Ge=Ge(SiMetBu2)2 1 was prepared by the reduction of the readily available 1,1-dichlorogermane (tBu2MeSi)2GeCl2 with potassium graphite. Compound 1 is a rather unusual example of a digermene featuring planar geometry at the doubly bonded germanium atoms, on the one hand, and an extraordinarily twisted Ge=Ge bond, on the other hand, caused by the electronic and steric factors of the bulky σ-donating silyl substituents. Although it maintains the structural integrity of its double bond in solution, 1 revealed reactivity that is not characteristic of the >Ge=Ge< bond but is typical for germylenes >Ge: upon reaction with nucleophilic reagents (isocyanide, orthoquinone). Unlike common alkenes, 1 affords stable cation and anion radicals generated by cyclic voltammetry.

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Tetrakis(di-tert-butylmethylsilyl)digermene: Synthesis, structure, electrochemical properties, and reactivity

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