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

Comprehensive Summary Two isomers of a sandwich‐type anion [Ge 9 ‐In‐Ge 9 ] 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 [Ge 9 ‐In‐Mo(CO) 5 ] 3– with a low‐valence In(I) center and an unsymmetrical sandwich‐type cluster {[(Ni@Ge 9 )In(Ni 0.648 @Ge 9 )]} 5– due to the insertion of Ni atoms, respectively. The isolation of these new derivatives demonstrates the reactivity of sandwich‐type [Ge 9 ‐In‐Ge 9 ] 5– acting as the precursor, which provides some enlightenment for constructing new inorganic sandwich compounds.