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The structures of group 14 C-metalated 6-amino-1-azafulvene dimers have been investigated in solution and in the solid state by NMR spectroscopy. For one of these compounds, 5,10-bis(dimethylamino)-3,8-bis(trimethylstannyl)-5H,10H-dipyrrolo[1,2-a: 1',2'-d]-pyrazine (2c), the molecular structure in the solid state has been determined by X-ray diffractometry. The two tin centers have a distorted-trigonal-bipyramidal co-ordination geometry with the more electronegative N ligand at a pseudoaxial position, resulting in one of the longest known Sn - N interactions: 3.101 (5) A°. Moreover, the temperature-dependent 13C CP-MAS NMR spectrum of this compound shows an appreciable narrowing of the Me3Sn signal between 296 and 333 K. By comparison with nonmetalated analogs or with isomer 5c, the nonreactivity of compound 2c toward hydrolytic decomposition into corresponding 5-(trimethylstannyl)-pyrrole-2-carbaldehyde (3c) may be the result of stabilization of the dimeric form 2c by a double Sn - N interaction. In silicon and germanium analogs (2a, 2b) the Si(Ge) - N interaction is weaker. |
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