| Abstract: | The reaction of InCl3 with LiAstBu2 in THF at –78 °C gives the indium arsenide Cl2InAstBu2 ( 1 ), which is dimer in solution and solid state. The corresponding reaction of InCl3 with Li2AstBu leads to the metalate Li(THF)4]2(InCl)4(InCl2)2(AstBu)6] ( 2 ). The arsanido metalate Li(THF)4]2(GaCl2)6(AstBu)4] · THF ( 3 · THF) could be obtained by treatment of GaCl3 with Li2AstBu in the molar ratio 6 : 4. A comparable reaction with TlCl3 and LiAsR2 or LiPR2, respectively, was not successful because of the oxidation potential of TlCl3. The reaction mixture of TlCl3 and LiPPh2 for example gives TlCl and Ph2P–PPh2 ( 4 ) as redox products. The octaarsane As(AstBu)3]2 ( 5 ) can be obtained by the treatment of tBuAs(SiMe3)2 with TlCl3 in THF. 1–5 were characterized by NMR, IR and MS techniques. The X‐ray analyses of 2 and 3 · THF show that 2 can be derived from the wurtzite structure while the zinc blende structure is the model for 3 with a adamantane‐like dianion (GaCl2)6(AstBu)4]2–. |
