Azametallatranes of group 14 elements. Syntheses and X-ray studies

Syntheses of a series of the title compounds, viz., N(CH 2 CH 2 NR) 3 M-X (1, M = Si, X = Me, R = SiMe 3 ; 2, M = Si, X = Et, R = SiMe 3 ; 3, M = Si, X = n-Bu, R = SiMe 3 ; 4, M = Si, X = vinyl, R = SiMe 3 ; 5, M = Si, X = Ph, R= SiMe 3 ; 6, M = Ge, X = Me, R = SiMe 3 ; 7, M = Ge, X = n-Bu, R = SiMe 3 ; 8, M = Ge, X = Ph, R = SiMe 3 ; 9, M = Sn, X = n-Bu, R = SiMe 3 ; 10, M = Sn, X = Ph, R = SiMe 3 ; 11, M = Si, X = vinyl, R = Me; 12, M = Ge, X = Me, R = Me) by the reaction of X-MCl 3 with N(CH 2 CH 2 NSiMe 3 Li) 3 or with N(CH 2 CH 2 NMeLi) 3 are reported. Reactions of the novel compounds X-Ge(NMe 2 ) 3 (15, X = Ph; 16, X = 1-naphthyl; 17, X = 9-antracenyl; 18, X = 9-phenantrenyl) with N(CH 2 CH 2 NHMe) 3 or N(CH 2 -CH 2 NH 2 ) 3 resulted in new 1-arylazagermatranes, N(CH 2 CH 2 NMe) 3 Ge-X (19, X = Ph; 20, X = 1-naphthyl; 21, X = 9-antracenyl; 22, X = 9-phenantrenyl) and N(CH 2 CH 2 NH) 3 Ge-X (23, X = Ph; 24, X = 1-naphthyl; 25, X = 9-phenantrenyl), respectively. 1-Phenylazager-matrane (23) is transformed to 8 by treatment with n-BuLi/Me 3 SiCl. Composition and structures of novel compounds were established by elemental analyses, 1 H, 1 3 C, and 2 9 Si NMR spectroscopy, and mass spectrometry. The X-ray structural studies of 10 and 19 clearly indicated the presence of a transannular interaction M←N a x for both compounds. quasi-Azametallatranes 5 and 8 possess extremely long M←N a x distances.