Synthesis and Characterization of Ternary Clusters Containing the [As 16 ] 10- Anion, [MM'As 16 ] 4- (M = Nb or Ta; M' = Cu or Ag).

The [Nb@As ₈ ] ^3- anion was first isolated from solution in 1986, and a number of isostructural [M@Pn ₈ ] ^{n -} clusters (M = Nb, Cr, or Mo; Pn = As or Sb; n = 2 or 3) have since been reported. We show here how anions of this class can be used as synthetic precursors that, in combination with sources of low-valent late transition metals (Cu and Ag), generate ternary polyarsenide cluster anions with unprecedented structural motifs. Chain type [MM'As ₁₆ ] ^4- (M = Nb or Ta; M' = Cu or Ag) units are found in compounds 2-5 . These clusters contain a nortricyclane-like As ₇ cage and a [M@As ₈ ] crown, linked by a single As atom, and represent a fusion of two quite distinct branches of polyarsenide chemistry. Our analysis of the electronic structure confirms that the cluster retains many of the features of the component units. Electrospray ionization mass spectrometry reveals a series of smaller component ions containing 8-12 As atoms, the density functional theory-computed structures of which can be understood in terms of the pseudoelement concept. This work not only presents a new type of coordination mode for As clusters but also offers a point of entry for the rational design of multinary arsenic-based materials.