Orientational Isomerism and Its Reactivity of a Main Group Sandwich Anion [Ge₉‐In‐Ge₉]^5–

Abstract

Comprehensive SummaryTwo isomers of a sandwich‐type anion [Ge9‐In‐Ge9]5– were synthesized by controlling the chelating agents (2,2,2‐crypt/18‐C‐6). Further reactions with early/late transition metal complexes, Mo(CO)6 and Ni(COD)2, respectively, yielded two new types of inorganic sandwich derivatives: a half‐sandwich cluster [Ge9‐In‐Mo(CO)5]3– with a low‐valence In(I) center and an unsymmetrical sandwich‐type cluster {[(Ni@Ge9)In(Ni0.648@Ge9)]}5– due to the insertion of Ni atoms, respectively. The isolation of these new derivatives demonstrates the reactivity of sandwich‐type [Ge9‐In‐Ge9]5– acting as the precursor, which provides some enlightenment for constructing new inorganic sandwich compounds.

Snap-shots of cluster growth: structure and properties of a Zintl ion with an Fe3 core, [Fe3Sn18]4−

“…1 Cluster fusion vs. cluster oligomerisation of E 9 polyhedra, E = Ge, Sn. [14][15][16][19][20][21][22][23][24][25][26][27][28][29] the extrusion of metal in the elemental form. A further complication is that the oxidative fusion of clusters is, at least in principle, in competition with oxidative oligomerisation via the formation of exo E-E bonds (Fig.…”

“…Larger clusters containing multiple transition metals are much less common but they offer the possibility of unusual magnetic phenomena and/or metal–metal bonding. Amongst the few known examples, 13 the Ge 18 series [Ni 2 InGe 18 ] 5− , 14 [Ni 3 Ge 18 ] 4− , 15 and [Pd 2 Ge 18 ] 4− (ref. 16 ) ( Fig.…”