Wang Yi, Zavalij Peter, Eichhorn Bryan
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742, USA.
Chem Commun (Camb). 2017 Oct 19;53(84):11600-11602. doi: 10.1039/c7cc07454a.
The norbornadiene-like bimetallic dimer [(ZnSb)] anion (1) was prepared by direct extraction from a ternary alloy with nominal composition "KZnSb" in ethylenediamine/toluene/2,2,2-crypt solutions. The structure represents a new type for coupled norbornadiene subunits, however, distortions around the Zn ions degrade the overall symmetry. The Zn ions achieve a 16e configuration and reside in near perfect ZnSb triangular coordination environments. DFT calculations reveal a 2.35 eV HOMO-LUMO gap and suggest covalent bonding between the Zn and Sb atoms.
类降冰片二烯双金属二聚体[(ZnSb)]阴离子(1)是通过在乙二胺/甲苯/2,2,2-穴醚溶液中从标称组成为“KZnSb”的三元合金直接萃取制备的。该结构代表了一种新型的耦合降冰片二烯亚基，然而，锌离子周围的畸变降低了整体对称性。锌离子达到16电子构型，并处于近乎完美的ZnSb三角配位环境中。密度泛函理论计算揭示了2.35 eV的最高占据分子轨道-最低未占分子轨道能隙，并表明锌和锑原子之间存在共价键。
