Synthesis and Structure of Tris(trialkylstannyl)‐ and Tris(dialkylhalostannyl)amines; Stabilization of the Sn3N Skeleton by Intramolecular Sn–X–Sn Bridges

Abstract

AbstractTris(triorganylstannyl)amines (R2R'Sn)3N (1, 2) with substituents R = R' = Me, Bu or R = Me and R' = iPr, tBu are obtained by metathesis from R2R'SnX and NaNH2 in liquid ammonia or by transamination of R3SnNMe2 with NH3. Tris(diorga‐nylhalostannyl)amines (R2XSn)3N (3) are synthesized by stannazane cleavage of (Me3Sn)3N (1) with R2SnX2. Information from multinuclear magnetic resonance spectra ascertain the planarity of the Sn3N skeleton of type 2 and 3, as well as the relationship between the coupling constants 1J(119Sn15N) and 2J(119Sn117Sn) and the Sn–N bond length as determined by the X‐ray structure analysis of 1, 3b and 3r. Compound 3b shows an almost undistorted D3h symmetry with a planar Br3Sn3N skeleton and SnN bond lengths of 1.99 Å, which beside those of 3a are the shortest found so far. According to MNDO approximate and ab initio calculations π interactions between the lone electron pair at the N atom and empty orbitals at the Sn atoms can be excluded. Therefore, the tristan‐nylamines discussed here have a trigonal planar nitrogen center with its lone electron pair in a p‐type orbital. Further characteristic features of the molecular structures of typ 3 compounds are the intramolecular Sn–X–Sn bridges (X = Cl, Br, I) found in the solid state as well as in solution. The molecular geometries of the tristannylamines are supported by MS fragmentation patterns as well as by infrared and Raman spectra.