First Examples of Au^I−X−Ag^I Halonium Cations (X = Cl and Br)

Novel {[(μ-PAnP)(AuX)2]2Ag}+SbF6- halonium ions (X = Cl, Br; PAnP = 9,10-bis(diphenylphosphino)anthracene) were synthesized from the reactions between (μ-PAnP)(AuX)2 and 1/2 mol equiv of AgSbF6. The compounds feature an unprecedented distorted Au4X4 dodecahedron which encapsulates a silver(I) ion at its center. The halonium ions are stabilized by collective actions of metallophilic Au−Ag, aromatic π−π, and Ag−X interactions.新型{[(μ-PAnP)(AuX)₂]₂Ag}⁺SbF₆⁻型卤鎓离子（halonium ions，其中X=Cl、Br；PAnP为9,10-双(二苯基膦)蒽）通过(μ-PAnP)(AuX)₂与0.5摩尔当量的六氟锑酸银（AgSbF₆）反应合成得到。该类化合物具有前所未有的畸变Au₄X₄十二面体结构，其中心包封有一个银(I)离子。此类卤鎓离子可通过亲金Au-Ag相互作用、芳香π-π相互作用以及Ag-X相互作用的协同作用实现稳定。