Isolation and Reactivity of Chlorotetryliumylidenes Using a Bidentate Bis(N-heterocyclic imine) Ligand,Organometallics

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Isolation and Reactivity of Chlorotetryliumylidenes Using a Bidentate Bis(N-heterocyclic imine) Ligand
Organometallics ( IF 2.5 ) Pub Date : 2020-08-25 , DOI: 10.1021/acs.organomet.0c00320
Florian S. Tschernuth ₁ , Franziska Hanusch ₁ , Tibor Szilvási ₂ , Shigeyoshi Inoue ₁

Affiliation

By use of the ethylene-bridged bidentate bis-NHI (NHI = N-heterocyclic imine) ligand 1 toward the complexation of ECl₂·(dioxane) (E = Ge, Sn) the synthesis of the first bis-NHI-stabilized chlorogermyliumylidene 2a[GeCl₃] and chlorostannyliumylidene 2b[SnCl₃] by Lewis base mediated autoionization was achieved. Using additional TMSOTf enabled the isolation of the corresponding triflate salts 2a[OTf] and 2b[OTf] in moderate yields. The obtained tetryliumylidene ions were fully characterized, including single-crystal X-ray diffraction analysis, and additionally investigated by density functional theory calculations. Reaction of 2a[OTf] with NaBH₄ led to the formation of a push–pull-stabilized hydridogermyliumylidene complex by Cl/H exchange. The same reaction with the stannyliumylidene led to transmetalation, yielding the corresponding dihydroboronium complex. Also, reactions with LiAlH₄ in both cases afforded the transmetalation product.

中文翻译：

用双齿双（N-杂环亚胺）配体分离和分离氯代叶绿素

通过使用乙烯桥联的双齿双-NHI（NHI = N-杂环亚胺）配体1进行ECl ₂ ·（二恶烷）（E = Ge，Sn）的络合，合成了第一个双-NHI稳定的氯锗亚苄基2a通过Lewis碱介导的自电离作用获得了[GeCl ₃ ]和氯代苯乙烯亚基2b [SnCl ₃ ]。使用额外的TMSOTf可以中等产率分离相应的三氟甲磺酸盐2a [OTf]和2b [OTf]。对获得的亚烷基离子进行了全面表征，包括单晶X射线衍射分析，并通过密度泛函理论计算进行了进一步研究。的反应NaBH _4的2a [OTf]导致通过Cl / H交换形成推挽稳定的氢化锗亚苄基复合物。与亚苯乙烯基亚烷基的相同反应导致金属转移，产生相应的二氢硼配合物。同样，在两种情况下与LiAlH _4的反应都提供了金属转移产物。

更新日期：2020-08-25

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