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Low‐Valent Germanylidene Anions: Efficient Single‐Site Nucleophiles for Activation of Small Molecules

Chris Gendy, J. Mikko Rautiainen, Aaron Mailman, Heikki M. Tuononen

2021Chemistry - A European Journal21 citationsDOIOpen Access PDF

Abstract

Abstract Rare mononuclear and helical chain low‐valent germanylidene anions supported by cyclic (alkyl)(amino)carbene and hypermetallyl ligands were synthesised by stepwise reduction from corresponding germylene precursors via stable and isolable germanium radicals. The electronic structures of the anions can be described with ylidene and ylidone resonance forms with the Ge−C π‐electrons capable of binding even weak electrophiles. The germanylidene anions reacted with CO 2 to give μ‐CO 2 ‐κ C :κ O complexes, a rare coordination mode for low‐valent germanium and inaccessible for the related neutral germylones. These results implicate low‐valent germanylidene anions as efficient single‐site nucleophiles for activation of small molecules.

Topics & Concepts

NucleophileChemistryElectrophileGermaniumMoleculeCarbeneAlkylPhotochemistryRadicalMedicinal chemistryStereochemistryInorganic chemistryCrystallographySiliconOrganic chemistryCatalysisSynthesis and characterization of novel inorganic/organometallic compoundsOrganoboron and organosilicon chemistryN-Heterocyclic Carbenes in Organic and Inorganic Chemistry
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