Synthesis and Characterization of 1-Allyl-3,7,10-trimethylgermatrane and 1-Allylazagermatranes

Abstract

The reaction between Br3GeAll (1) and N(CH2CHMeOSnBu3)3 (2, mixture of isomers) yielded N(CH2CHMeO)3GeAll (3) as a mixture of diastereomers. Three azagermatranes of the type N(CH2CH2NR)3GeAll (9, R = H; 10, R = Me; 11, R = Me3Si) have been synthesized from the reaction of (Me2N)3GeAll (5) with N (CH2CH2NHR)3 (R = H, 6; Me, 7; Me3Si, 8). Composition and structures of the new compounds were established by elemental analyses, 1H and 13C NMR spectroscopy and mass spectrometry.

Synthesis and Characterization of Group 14 1-Haloazametallatranes

“…MHal 4 (M ϭ Si, Ge, Sn; Hal ϭ Cl, Br) (Aldrich) were used as supplied. Starting materials Me 3 -tren [28] and TMS 3 -tren [12] were prepared according to the literature. C 6 D 6 was obtained from Deutero GmbH and dried over sodium.…”

“…[2] The corresponding azastannatranes (B, R ϭ SiMe 3 ) are as yet unknown and for germanium only N(CH 2 CH 2 NSiMe 3 ) 3 GeϪallyl has been reported amongst the N(CH 2 CH 2 NSiMe 3 ) 3 GeϪX derivatives prior to this work. [12] In this paper we report on the synthesis of 1-haloazametallatranes (M ϭ Ge, Sn) by metathetical exchange reactions between MHal 4 (M ϭ Ge, Sn; Hal ϭ Cl, Br) and the trilithium salts of the parent amines N(CH 2 CH 2 NHMe) 3 (Me 3 -tren) and N(CH 2 CH 2 NHSiMe 3 ) 3 (TMS 3 -tren). Details of the X-ray crystal and molecular structures of N(CH 2 CH 2 NMe) 3 GeCl (1) and N(CH 2 CH 2 NSiMe 3 ) 3 GeCl (3) are also described.…”

Azametallatranes of Group 14 Elements. Syntheses and X-ray Studies

“…As a part of our program to investigate the chemical behavior of both metallatranes and azametallatranes and the degree of strength of the transannular M←N interactions in these compounds, − we recently reported a new approach to 1-haloazagermatranes and 1-haloazastannatranes, viz., treatment of MHal 4 (M = Ge, Sn) with N(CH 2 CH 2 NMeLi) 3 (Li 3 -Me-tren) and with N(CH 2 CH 2 NSiMe 3 Li) 3 (Li 3 -Me 3 Si-tren) . In this report we present the use of lithium salts Li 3 -Me-tren and Li 3 -Me 3 Si-tren in metathetical reactions of these salts with X−MCl 3 (M = Si, Ge, Sn) for the synthesis of 1-alkyl-, 1-vinyl-, and 1-arylazametallatranes of the group 14 elements.…”

Syntheses and Characterization of 1-Haloazagermatranes

“…First examples of azagermatranes, NXCFLCFLNR^GeX (R = H, Me; X = Me, tert-Bu, NMe2), have been reported as late as 1993 [3]. Recently we have described new azagermatranes, N(CH2CH2NR)3GeAllyl (R = H, Me, SiMe3) [4], We were now interested to find a simple route to 1 -haloazagermatranes and to com pare their reactivity with that of 1 -halogermatranes [1,5] and 1-haloazasilatranes [6 ]. In this context, we here report the syntheses and some preliminary ex periments on the reactivity of 1 -haloazagermatranes (1 -4) in order to obtain information on nucleophilic substitution reactions at the penta-coordinated ger manium atom.…”