Tremmel Jakub, Tydlitát Jiří, Dostál Libor, Růžička Aleš, Deraet Xavier, Turek Jan, Jambor Roman
Department of General and Inorganic Chemistry, University of Pardubice, 53210, Pardubice, Czech Republic.
Institute of Organic Chemistry and Technology, University of Pardubice, 53210, Pardubice, Czech Republic.
Chemistry. 2020 May 12;26(27):6070-6075. doi: 10.1002/chem.202000970. Epub 2020 Apr 28.
The reactions of monomeric C,N-chelated organogermanium(II) hydride L(H)Ge⋅BH with organolithium salts RLi yielded lithium hydrogermanatoborates (Li(THF) {BH [L(H)GeR]}) . Compound (Li(THF) {BH [L(H)GePh]}) 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⋅BH . The interaction of (Li(THF) {BH [L(H)GePh]}) 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) {BH [L(H)GePh]}) 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⋅BH with PhLi in nonpolar solvents.
单体C，N - 螯合氢化有机锗（II）L（H）Ge⋅BH与有机锂盐RLi反应生成氢锗硼酸盐锂（Li（THF）{BH [L（H）GeR]}）。化合物（Li（THF）{BH [L（H）GePh]}）用作LiH的来源，用于在非极性溶剂中还原有机C = O或C = N键，同时消除中性配合物L（Ph）Ge⋅BH。通过计算研究进一步研究了（Li（THF）{BH [L（H）GePh]}）与极性C = O键的相互作用，揭示了预反应中间体的合理几何结构。实验和理论研究表明，尽管（Li（THF）{BH [L（H）GePh]}）的Li原子与C = O键配位，但GeH片段是还原反应中的活性物种。最后，在非极性溶剂中，L（H）Ge⋅BH与PhLi的混合物还原了苯甲醛。
