As3M(As3Pb3)]3− (M = Nb, Ta): Ternary Heterometallic Clusters with Early Transition Metal Atoms and Aromatic [Pb3]2−

Abstract

Main observation and conclusionTwo ternary clusters, [As3Nb(As3Pb3)]3− 1 and [As3Ta(As3Pb3)]3− 2, were directly extracted from “K8NbPbAs5” and “K8TaPbAs5” intermetallic solid in the presence of ethylenediamine and 2.2.2‐crypt, respectively. Both 1 and 2, comprising an electron‐poor early transition metal‐atom Nb or Ta coordinated to a As3 triangle and a bowl‐like As3Pb3, were characterized by single crystal X‐ray diffraction, energy dispersive X‐ray (EDX) and electrospray ionization mass‐spectrometry (ESI‐MS). They also represent the first examples of the Pb‐As hybrid in solution‐based Zintl anion chemistry and DFT calculations revealed a σ‐aromaticity of the [Pb3]2− unit.