Synthesis and Characterisation of Novel Main Group Element Clusters with Tin‐Phosphorus, Tin‐Arsenic, and Germanium‐Phosphorus Skeletons

The reaction of i Pr 3 SiPLi 2 with SnCl 2 in the mol ratio 1:1 leads to the formation of [Sn 7 (PSi i Pr 3 ) 7 ] ( 1 ). The cluster [Sn 8 (PSi i Pr 3 ) 6 Cl 2 ] ( 3 ) is obtained, if the same reaction is carried out with a slight excess of the metal salt. Similar lithium chloride elimination reactions between SnCl 2 and i Pr 3 SiAsLi 2 in the mol ratio 1:1 and 2:3, however, yield [Sn 7 (AsSi i Pr 3 ) 7 ] ( 2 ) and [Sn 4 (AsSi i Pr 3 ) 6 Li 4 (Et 2 O) 2 ] ( 4 ), respectively. The metal salt GeCl 2 (diox) 2 (diox = 1,4‐dioxane) reacts with i Pr 3 SiPLi 2 to give [Ge 6 (PSi i Pr 3 ) 6 ] ( 5 ). Compounds 1 − 5 were characterised by NMR and IR spectroscopic techniques as well as elemental analysis. The crystal structures were identified by X‐ray diffraction analysis, which confirmed that the heptameric skeletons of 1 and 2 are structurally analogous. The Sn/P cluster 3 contains subvalent tin atoms, while 4 forms a Sn 4 As 6 Li 4 rhombododecahedron and 5 a slightly distorted hexagonal prism. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)