Synthesis and Characterization of the Highly Unstable Metalloid Cluster Ag64(PnBu3)16Cl6

The reduction of (nBu3P)AgCl with LiBH(sBu)3 in toluene gives the metalloid silver cluster Ag64(PnBu3)16Cl6 (1) as dark red, temperature‐ and light‐sensitive single crystals in high yield. 1 is the largest structurally characterized metalloid silver cluster exhibiting chlorine and phosphine substituents only. The silver atoms in 1 show an overall brick‐shape arrangement, where structural resemblance to the close‐packed fcc and hcp structures is realized. Within 1 a 58 electron closed shell system is present. The light sensitivity renders 1 as a model compound for the primary seeds of the photo process, whereby this sensitivity, together with the high‐yield synthesis show that 1 is a perfect starting compound for further investigations like silver‐plating processes. Light up the dark! The reduction of (nBu3P)AgCl with LiBH(sBu)3 in toluene gives the highly unstable metalloid silver cluster Ag64(PnBu3)16Cl6 as dark red, temperature‐ and light‐sensitive single crystals in high yield. This is the largest structurally characterized metalloid silver cluster exhibiting chlorine and phosphine substituents only.