Abstract: | Influence of the Ring Atoms on the Structure of Triel‐Pentel Heterocycles – Synthesis and X‐Ray Crystal Structures of [Me2InAs(SiMe3)2]2 and [Me2InSb(SiMe3)2]3 Triel‐pentel heterocycles [Me2InE(SiMe3)2]x have been prepared by dehalosilylation reactions from Me2InCl and E(SiMe3)3 (E = As, x = 2; E = Sb, x = 3) and characterised by NMR spectroscopy and by X‐ray crystal structure analyses. In addition the X‐ray crystal structures of [Me2GaAs(SiMe3)2]2 and [Me2InP(SiMe3)2]2 are reported. The compounds complete a family of 13 identically substituted heterocycles [Me2ME(SiMe3)2]x (M = Al, Ga, In; E = N, P, As, Sb, Bi; x = 2, 3), whose structures were investigated depending on the ring atoms M and E. The tendencies that have been observed concerning the ring sizes can be explained by the interplay of the atomic radii of the central atoms and the sterical demand of the ligands. After a formal separation of the M–E bonds in σ bonds and dative bonds the characteristic differences and trends in the endocyclic and exocyclic bond angles of both centres M and E can be interpreted on the basis of a simple Lewis acid/base adduct model. |