重双氮烯自由基阴离子的合成、结构及键合性质
Synthesis, structure and bonding nature of heavy dipnictene radical anions.
作者信息
Weinert Hanns M, Wölper Christoph, Haak Julia, Cutsail George E, Schulz Stephan
机构信息
Institute for Inorganic Chemistry, Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen Universitätsstraße 5-7 45117 Essen Germany
Max Planck Institute for Chemical Energy Conversion (CEC) Stiftstraße 34-36 45470 Mülheim a. d. Ruhr Germany.
出版信息
Chem Sci. 2021 Aug 30;12(42):14024-14032. doi: 10.1039/d1sc04230k. eCollection 2021 Nov 3.
Cyclic voltammetry (CV) studies of two L(X)Ga-substituted dipnictenes [L(RN)GaE] (E = Sb, R = Me ; E = Bi; R = Et ; L = HC[C(Me)NDipp]; Dipp = 2,6--PrCH) showed reversible reduction events. Single electron reduction of and with KC in DME in the presence of benzo-18-crown-6 (B-18-C-6) gave the corresponding dipnictenyl radical anions (DME)[K(B-18-C-6)][L(RN)GaE] (E = Sb, R = Me ; E = Bi, R = Et ). Radical anions and were characterized by EPR, UV-vis and single crystal X-ray diffraction, while quantum chemical calculations gave deeper insight into the nature of the chemical bonding.
对两种L(X)Ga取代的双氮烯[L(RN)GaE]（E = Sb，R = Me；E = Bi，R = Et；L = HC[C(Me)NDipp]；Dipp = 2,6 - -PrCH）进行的循环伏安法（CV）研究显示出可逆的还原过程。在18 - 冠 - 6（B - 18 - C - 6）存在下，于二甲醚（DME）中用KC对 和 进行单电子还原，得到相应的双氮烯基自由基阴离子（DME）[K(B - 18 - C - 6)][L(RN)GaE]（E = Sb，R = Me；E = Bi，R = Et）。通过电子顺磁共振（EPR）、紫外 - 可见光谱（UV - vis）和单晶X射线衍射对自由基阴离子 和 进行了表征，而量子化学计算则更深入地揭示了化学键的本质。
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