Game of Dice: Synthesis and Characterisation of Molecular Compounds of the Systems Sn/E and Pb/E (E = P/As)

The heterocubane‐like molecules [ t Bu 2 PhSiESn] 4 (E = P ( 2 ), As ( 3 )) and [(Me 3 Si) 3 SiP M ] 4 ( M = Sn ( 4 ), Pb ( 5 )) were obtained by the reaction of primary silyl phosphines or ‐arsines with M {N(SiMe 3 ) 2 } 2 . Likewise, the reactions of the miscellaneously substituted arsine (Me 3 Si) 3 SiAs(SiMe 3 ) 2 ( 1 ) with M Cl 2 yielded the heterocubane species [(Me 3 Si) 3 SiAs M ] 4 ( M = Sn ( 8 ), Pb ( 9 )). The unique cage compounds [( t Bu 2 PhSiAs) 4 Sn 3 LiOEt 2 ] – [Li(Et 2 O) 4 ] + ( 6 ) and [( t Bu 2 PhSiAsSn) 4 SnCl(Bu)] 4 ( 7 ) could be obtained in a metathesis reaction of SnCl 2 with the lithiated silylarsine t Bu 2 PhSiAsLi 2 in different stoichiometric percentages.