Institut für Anorganische Chemie , Universität Tübingen , Auf der Morgenstelle 18 , 72076 Tübingen , Germany.
Inorg Chem. 2019 Dec 2;58(23):15758-15768. doi: 10.1021/acs.inorgchem.9b01822. Epub 2019 Aug 1.
Terphenyltin and terphenylgermanium trihydrides were deprotonated in reaction with strong bases, such as LiMe, LDA, or KBn. In the solid state, the Li salts of the germate anion and exhibit a Li-Ge contact. In the Li salt of the dihydridostannate anion , the Li cation is not coordinated at the tin atom instead an interaction of the Li cation with the hydride substituents was found. Evidenced by H-Li-HOESY NMR spectroscopy the Li-salt of the deprotonated tin hydride exhibits in toluene solution a contact between Li cation and hydride substituents, whereas in the H-Li-HOESY NMR spectrum of the homologous germate salt , no crosspeak between hydride and Li signals was found. The organodihydridogermate and -stannate react as nucleophiles with low-valent Group 14 electrophiles. Thus, three compounds were synthesized: Ar-Ë'-EH-Ar (E', E = Sn, Ge; Pb, Ge; Pb, Sn; Ar = Ar', Ar*). Following an alternative synthesis Ar'SnHPbAr* was synthesized in reaction between [(ArPbH)] and [(Ar'SnH)] generated in situ. In reaction between low-valent organotin hydride [(ArSnH)] and organdihydridostannate [ArSnH] formation of distannate [ArSnH] was found.
三联苯锡和三联苯锗三氢化物在强碱如 LiMe、LDA 或 KBn 的作用下脱质子。在固态下，锗酸根阴离子 和 的 Li 盐表现出 Li-Ge 接触。在二氢二锡酸根阴离子 的 Li 盐中，Li 阳离子没有配位在锡原子上，而是发现 Li 阳离子与氢化物取代基之间存在相互作用。通过 H-Li-HOESY NMR 光谱学证明，在甲苯溶液中，脱质子锡氢化物的 Li 盐表现出 Li 阳离子和氢化物取代基之间的接触，而在同源锗酸盐的 H-Li-HOESY NMR 光谱中，没有发现氢化物和 Li 信号之间的交叉峰。有机二氢锗酸盐和锡酸盐作为亲核试剂与低价第 14 族电子体反应。因此，合成了三种化合物：Ar-Ë'-EH-Ar（E'，E=Sn，Ge；Pb，Ge；Pb，Sn；Ar=Ar'，Ar*）。通过在 [(ArPbH)] 和 [(Ar'SnH)] 原位生成之间的反应，合成了 Ar'SnHPbAr。在低价有机锡氢化物 [(ArSnH)] 和有机二氢锡酸盐 [ArSnH] 之间的反应中，发现了锡酸盐 [Ar*SnH] 的形成。
