Synthesis of Heavy N‐ Heterocyclic Tetrylenes: Influence of Ligand Sterics on Structure

The synthesis and structural characterisation of [(NON R )M] (NON=O(SiMe 2 NR) 2 ] 2− ; R= t Bu, Ph, 2,6‐Me 2 C 6 H 3 (Dmp), 2,6‐ i Pr 2 C 6 H 3 (Dipp); M=Ge, Sn, Pb) is described. Germanium complexes [(NON Ph )Ge], [(NON Dmp )Ge] and [(NON Dipp )Ge] are monomeric. Tin complexes [(NON Ph )Sn] 2 , [(NON Dmp )Sn] 2 and [(NON t Bu )Sn] 2 are dimeric in the solid‐state, with [(NON Ph )Sn] 2 forming a link through bridging N‐atoms, [(NON Dmp )Sn] 2 linked through Sn⋅⋅⋅Ar contacts and [(NON t Bu )Sn] 2 forming the first distannene bearing two amido ligands. In contrast, [(NON Dipp )Sn] is monomeric in the solid‐state. The lead complexes [(NON Ph )Pb] 2 and [(NON Dmp )Pb] 2 are isostructual with their tin analogues while [(NON t Bu )Pb] is monomeric in the solid‐state. Solution phase NMR spectroscopic data suggest that all [(NON R )M] compounds are monomeric in solution. Structural parameters, including buried volume (%V bur ) are discussed.