Synthesis and Structure of Binary Copper/Silver-Arsenic Clusters Derived from Zintl Ion As_(7)^(3-)

Polyarsenides containing coinage metals,[As_(7)Cu(PPh_(3))]^(2-)(1)and[M_(2)As_(14)]^(4-)(M=Cu,2;Ag,3),were synthesized by reactions of the nominal composition K_(3)As_(7) with Group 11 metal complexes.The possible intermediate,cluster 1,was isolated from the solution phase through subtle changes in reaction conditions in the formation process of complex 2.Hence,we establish the pathway of the bimetallic bridged clusters[Cu_(2)As_(14)]^(4-)by the oxidation of the[As_(7)Cu(PPh_(3))]^(2-).Quantum chemical calculations reveal the presence of metallophilic interaction in clusters 2 and 3.

Ruthenium-mediated assembly and enhanced stability of heterometallic polystannides[Ru_(2)Sn_(19)]^(4−)and[Ru_(2)Sn_(20)]^(6−)

In this work,we report the synthesis and characterization of two novel Ru-containing Zintl clusters:[Sn_(19){Ru(COD)(en)}_(2)]^(4−)and[Sn_(20){Ru(COD)}_(2)]^(6−).The synthesized compounds not only expand the family of Ru-Sn cluster systems but also shed light on the structure of heterometallic complexes in a previously unknown range of tin atoms.The single-crystal X-ray diffraction(XRD)analysis reveals the dimeric nature of the clusters.Two different assembly patterns of the formal[Sn(η^(3)-Sn_(9))]monomer were observed:the dimerization through the vertex fusion process and the direct dimerization through the formation of 2c–2e Sn–Snσbond.For both clusters,the density functional theory calculations reveal the locallyσ-aromatic nature of the[Sn(η^(3)-Sn_(9))]monomer resulting in two independent magnetic shielding cones.We believe that our findings will help the community to further explore the fascinating chemistry of polystannide clusters.