Syntheses and Characterization of 1-Haloazagermatranes

Abstract

Germanium, Azagermatranes The reaction of tris(dimethylamino)halogermanes, (Me?N)3GeHal (7, Hal = Cl; 8 , Hal = Br), with tris(2-aminoethyl)amines, N(CH2CH2NHR)3 (5, R = H; 6 , R = Me), yield l-halo-N,N',N"-azagermatranes (1, X = Cl, R = H; 2, X = Br, R = H; 3, X = Cl, R = Me; 4, X = Br, R = Me). Treatment of 4 with n-butyllithium affords l-n-butyl-N,N',N"-trimethylazagermatrane (14) in high yield. Reactions of n-BuLi with 7 or (Me2N)4Ge (13) lead to the formation of (Me2N)3Ge-n-Bu (15). On treatment of 15 with 5 the 1 -n-butylazagermatrane 16 was obtained. The molecular composition and the structures of all new compounds were established by elemental analyses, 'H and 13C NMR spectroscopy and mass spectrometry.

Synthesis and Characterization of Group 14 1-Haloazametallatranes

“…1 H NMR, 13 C NMR and EI MS data were consistent with those already reported. [13] 1-Chloro-N,NЈ,NЈЈ-tris(trimethylsilyl)azagermatrane (3): A 1.6  nBuLi solution in hexane (4.67 mL, 7.5 mmol) at room temperature was added dropwise to a stirred solution of TMS 3 -tren (0.90 g, 2.5 mmol) in 40 mL of toluene. The reaction mixture was stirred for 5 h and a solution of GeCl 4 (0.53 g, 2.5 mmol) in 10 mL of toluene was added dropwise at room temperature.…”

“…[16,21] We prepared azagermatranes 1 and 2 by transamination reactions of HalGe(NMe 2 ) 3 with Me 3 -tren. [13] Another method for building the main group element azatrane framework was previously only used for transition metals. [22] Tetrahalides (Hal ϭ Cl, Br) of germanium and tin react readily with the trilithium salts of Me 3 -tren and TMS 3 -tren (in toluene at room temperature) to give 1-haloazametallatranes 1Ϫ8 in high yield (Scheme 2).…”

“…[13] 1-Bromo-N,NЈ,NЈЈ-trimethylazagermatrane (2): Following the same experimental procedure as above for 1 using Me 3 -tren (0.50 g, 2.7 mmol), a 1.6  nBuLi solution in hexane (5.06 mL, 8.1 mmol) and GeBr 4 (1.04 g, 2.7 mmol), colourless crystals (0.63 g, 69%) were obtained. 1 H NMR, 13 C NMR and EI MS data were consistent with those already reported. [13] 1-Chloro-N,NЈ,NЈЈ-tris(trimethylsilyl)azagermatrane (3): A 1.6  nBuLi solution in hexane (4.67 mL, 7.5 mmol) at room temperature was added dropwise to a stirred solution of TMS 3 -tren (0.90 g, 2.5 mmol) in 40 mL of toluene.…”

“…1 H NMR (C 6 D 6 , 200.13 MHz): δ ϭ 0.38 (s, 27 H, SiCH 3 ), 1.81 (t, 1 J ϭ 6 Hz, 6 H, CH 2 N), 2.71 (t, 1 J ϭ 6 Hz, 6 H, CH 2 NSi) ppm. 13 C NMR (C 6 D 6 , Attempted Syntheses of N(CH 2 CHNR) 3 Si؊Hal: Reactions of trilithium salts of Me 3 -tren and TMS 3 -tren with SiCl 4 and SiBr 4 were carried out as for 1 and 3, respectively, resulting (according to 1 H NMR spectra) in a complex mixture of products which were difficult to separate and to identify.…”

“…Hz, 6 H, CH 2 N), 2.59 (t, 1 J ϭ 6 Hz, 6 H, CH 2 NSi) ppm 13. C NMR (C 6 D 6 , 50.32 MHz): δ ϭ 2.41 (SiCH 3 ), 41.03 (CH 2 N), 58.79 (CH 2 NSi) ppm.…”