Organogermanium(II) Hydrides as a Source of Highly Soluble LiH. Issue 27 (28th April 2020)

• Record Type: Journal Article
• Authors: Tremmel, Jakub; Tydlitát, Jiří; Dostál, Libor; Růžička, Aleš; Deraet, Xavier; Turek, Jan; Jambor, Roman
• Is Part Of: Chemistry. Volume 26:Issue 27(2020)
• Page Start: 6070
• Page End: 6075
• Publication Date: 2020-04-28
• Subjects: density functional calculations -- germanium -- hydrides -- lithium -- reduction; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202000970
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The reactions of monomeric C, N‐chelated organogermanium(II) hydride L(H)Ge⋅ BH3 with organolithium salts RLi yielded lithium hydrogermanatoborates (Li(THF)2 {BH3 [L(H)GeR]})2 . Compound (Li(THF)2 {BH3 [L(H)GePh]})2 was used as a source of LiH for the reduction of organic C=O or C=N bonds in nonpolar solvents accompanied by the elimination of a neutral complex L(Ph)Ge⋅ BH3 . The interaction of (Li(THF)2 {BH3 [L(H)GePh]})2 with the polar C=O bond was further investigated by computational studies revealing a plausible geometry of a pre‐reactive intermediate. The experimental and theoretical studies suggest that, although the Li atom of (Li(THF)2 {BH3 [L(H)GePh]})2 coordinates the C=O bond, the GeH fragment is the active species in the reduction reaction. Finally, benzaldehyde was reduced by a mixture of L(H)Ge⋅ BH3 with PhLi in nonpolar solvents. Abstract : Soluble lithium hydride source : The reduction of C=Y polar bonds by RLi in the presence of monomeric germanium hydride is possible. The combination of PhLi with L(H)Ge⋅ BH3 yielded (Li(THF)2 {BH3 [L(H)GePh]})2 (3 ), which acts as a source of LiH for the reduction of benzaldehyde in non‐polar solvents. The reaction proceeds via intermediate 3INT accompanied by the elimination of neutral complex L(Ph)Ge⋅ BH3 (6 ).