Helling Christoph, Cutsail George E, Weinert Hanns, Wölper Christoph, Schulz Stephan
Institute for Inorganic Chemistry and 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 an der Ruhr, Germany.
Angew Chem Int Ed Engl. 2020 May 4;59(19):7561-7568. doi: 10.1002/anie.202000586. Epub 2020 Mar 10.
We report on the structures of three unprecedented heteroleptic Sb-centered radicals L(Cl)GaSb (2-R, R=B[N(Dip)CH] 2-B, 2,6-Mes C H 2-C, N(SiMe )Dip 2-N) stabilized by one electropositive metal fragment [L(Cl)Ga] (L=HC[C(Me)N(Dip)] , Dip=2,6-i-Pr C H ) and one bulky B- (2-B), C- (2-C), or N-based (2-N) substituent. Compounds 2-R are predominantly metal-centered radicals. Their electronic properties are largely influenced by the electronic nature of the ligands R, and significant delocalization of unpaired-spin density onto the ligands was observed in 2-B and 2-N. Cyclic voltammetry (CV) studies showed that 2-B undergoes a quasi-reversible one-electron reduction, which was confirmed by the synthesis of [K([2.2.2]crypt)][L(Cl)GaSbB[N(Dip)CH] ] ([K([2.2.2]crypt)][2-B]) containing the stibanyl anion [2-B] , which was shown to possess significant Sb-B multiple-bonding character.
我们报道了三种前所未有的杂配型以锑为中心的自由基L(Cl)GaSb（2-R，R = B[N(Dip)CH]₂-B、2,6-Mes₂C₆H₂-C、N(SiMe₃)Dip₂-N）的结构，它们由一个电正性金属片段[L(Cl)Ga]（L = HC[C(Me)N(Dip)]₂，Dip = 2,6-i-Pr₂C₆H₃）和一个大位阻的硼基（2-B）、碳基（2-C）或氮基（2-N）取代基稳定。化合物2-R主要是以金属为中心的自由基。它们的电子性质在很大程度上受配体R的电子性质影响，并且在2-B和2-N中观察到未成对自旋密度显著离域到配体上。循环伏安法（CV）研究表明2-B经历了一个准可逆的单电子还原过程，这通过合成含有亚锑基阴离子[2-B]⁻的[K([2.2.2]crypt)][L(Cl)GaSbB[N(Dip)CH]₂]（[K([2.2.2]crypt)][2-B]⁻）得以证实，该化合物显示具有显著的Sb-B多重键特征。
