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] |
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| Authors: | Christina Fischer Wilhelm Klein Thomas F. Fässler |
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| Affiliation: | Department of Chemistry, Technische Universit?t München, Garching, Germany |
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| Abstract: | Novel silylation reactions at [Ge9] Zintl clusters starting from the chlorosilanes SiR3Cl (R = iBu, iPr, Et) and the Zintl phase K4Ge9 are reported. The formation of the tris‐silylated anions [Ge9(SiR3)3]– [R = iBu ( 1a ), iPr ( 1b ), Et ( 1c )] by heterogeneous reactions in acetonitrile was monitored by ESI‐MS measurements. For R = iBu 1H, 13C and 29Si NMR experiments confirmed the exclusive formation of 1a . Subsequent reactions of 1a with CuNHCDippCl and Au(PPh3)Cl result in formation of the neutral metal complex (CuNHCDipp)[Ge9{Si(iBu)3}3]·0.5 tol ( 2 ·0.5 tol) and the metal bridged dimeric unit {Au[Ge9{Si(iBu)3}3]2}– ( 3a ), isolated as a (K‐18c6)+ salt in (K‐18c6)Au[Ge9{Si(iBu)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[Ge9{Si(iBu)3}2]·tol ( 4 ·tol), containing the bis‐silylated cluster anion [Ge9(Si(iBu)3)2]2– ( 4a ), were obtained. The compounds 2 ·0.5 tol, 3 ·tol and 4 ·tol were characterized by single‐crystal structure determination. |
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| Keywords: | Germanium Silanes Functionalization Coinage Metals Zintl clusters |
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