The Imino Stannylene SnNH Incorporated in a Molecular Tin‐Nitrogen Cage and other Tin(II)‐Nitrogen Derivatives

The iminostannylene HNSn was successfully incorporated in a molecular cage of composition (Me 2 R Si–NSn) 3 (HNSn) with group R either being a methyl ( 1 ) or vinyl ( 2 ) substituent. An X‐ray structure analysis reveals that 2 consists of a distorted Sn 4 N 4 cube. The Sn–N(H) bond lengths [2.189(2) Å] are in the range for Sn 4 N 4 hetero cubanes. When stored in a toluene solution the clusters 1 and 2 decompose slowly into the symmetric cubanes (Me 2 R Si–NSn) 4 [ R = Me ( 3 ), CHCH 2 ( 4 )] and an amorphous and insoluble powder of composition HNSn. The decomposition follows a first order rate law as established for 2 with a half life time t 1/2 = 320 d at 20 °C. The compounds 1 and 2 can thus be regarded as a result of interaction between three entities {Me 2 R Si–NSn} and one entity {HNSn}. We also isolated the twistane‐like Me 2 Si(NtBu) 2 Sn 2 NtBu ( 5 ) in a crystalline form. The central structure of this molecule, which has almost C 2 v symmetry, has a trigonal bipyramid Sn 2 N 3 unit with the nitrogen atoms occupying the equatorial plane. Each nitrogen atom has a tert ‐butyl ligand and two of the N atoms are further connected by the dimethylsilyl group. There is one nitrogen atom in an almost planar environment (only bonding to tert ‐butyl and two tin atoms) with a remarkable short Sn–N bond length of 2.048(5) Å. Both tin atoms in cage 5 can bond to Cr(CO) 5 to form [Me 2 Si(NtBu) 2 Sn 2 N t Bu][Cr(CO) 5 ] 2 ( 6 ) with an almost linear Cr–Sn ··· Sn–Cr arrangement and Sn–Cr bond lengths of 2.581(1) Å (X‐ray diffraction).