Functionalization of [Ge9] with Small Silanes:[Ge9(SiR3)3]– (R = iBu, iPr, Et) and the Structures of (CuNHCDipp)[Ge9{Si(iBu)3}3], (K‐18c6)Au[Ge9{Si(iBu)3}3]2, and (K‐18c6)2[Ge9{Si(iBu)3}2]. Issue 24 (15th November 2016)

• Record Type: Journal Article
• Authors: Schiegerl, Lorenz J.; Geitner, Felix S.; Fischer, Christina; Klein, Wilhelm; Fässler, Thomas F.
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 642:Issue 24(2016)
• Page Start: 1419
• Page End: 1426
• Publication Date: 2016-11-15
• Subjects: Germanium; Silanes; Functionalization; Coinage Metals; Zintl clusters; Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201600295
• Languages: English
• ISSNs: 0044-2313

Abstract

Abstract : Novel silylation reactions at [Ge9 ] Zintl clusters starting from the chlorosilanes SiR3 Cl (R = i Bu, i Pr, Et) and the Zintl phase K4 Ge9 are reported. The formation of the tris‐silylated anions [Ge9 (SiR3 )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 of1a . Subsequent reactions of1a with CuNHC Dipp Cl and Au(PPh3 )Cl result in formation of the neutral metal complex (CuNHC Dipp )[Ge9 {Si( i Bu)3 }3 ]·0.5 tol (2 ·0.5 tol) and the metal bridged dimeric unit {Au[Ge9 {Si( i Bu)3 }3 ]2 } – (3a ), isolated as a (K‐18c6) + salt in (K‐18c6)Au[Ge9 {Si( i Bu)3 }3 ]2 ·tol (3 ·tol), respectively. Finally, from a toluene/hexane solution of1a in presence of 18‐crown‐6, crystals of the compound (K‐18c6)2 [Ge9 {Si( i Bu)3 }2 ]·tol (4 ·tol), containing the bis‐silylated cluster anion [Ge9 (Si( i Bu)3 )2 ] 2– (4a ), were obtained. The compounds2 ·0.5 tol, 3 ·tol and4 ·tol were characterized by single‐crystal structure determination. Abstract :