Functionalization of [Ge 9 ] with Small Silanes:[Ge 9 (SiR 3 ) 3 ] – (R = i Bu, i Pr, Et) and the Structures of (CuNHC Dipp )[Ge 9 {Si( i Bu) 3 } 3 ], (K‐18c6)Au[Ge 9 {Si( i Bu) 3 } 3 ] 2 , and (K‐18c6) 2 [Ge 9 {Si( i Bu) 3 } 2 ]

Novel silylation reactions at [Ge 9 ] Zintl clusters starting from the chlorosilanes SiR 3 Cl (R = i Bu, i Pr, Et) and the Zintl phase K 4 Ge 9 are reported. The formation of the tris‐silylated anions [Ge 9 (SiR 3 ) 3 ] – [R = i Bu ( 1a ), i Pr ( 1b ), Et ( 1c )] by heterogeneous reactions in acetonitrile was monitored by ESI‐MS measurements. For R = i Bu 1 H, 13 C and 29 Si NMR experiments confirmed the exclusive formation of 1a . Subsequent reactions of 1a with CuNHC Dipp Cl and Au(PPh 3 )Cl result in formation of the neutral metal complex (CuNHC Dipp )[Ge 9 {Si( i Bu) 3 } 3 ]·0.5 tol ( 2 ·0.5 tol) and the metal bridged dimeric unit {Au[Ge 9 {Si( i Bu) 3 } 3 ] 2 } – ( 3a ), isolated as a (K‐18c6) + salt in (K‐18c6)Au[Ge 9 {Si( i Bu) 3 } 3 ] 2 ·tol ( 3 ·tol), respectively. Finally, from a toluene/hexane solution of 1a in presence of 18‐crown‐6, crystals of the compound (K‐18c6) 2 [Ge 9 {Si( i Bu) 3 } 2 ]·tol ( 4 ·tol), containing the bis‐silylated cluster anion [Ge 9 (Si( i Bu) 3 ) 2 ] 2– ( 4a ), were obtained. The compounds 2 ·0.5 tol, 3 ·tol and 4 ·tol were characterized by single‐crystal structure determination.