Abstract:Germanium, Germatrane, Organotin Reagents, X-Ray Data, NM R Data 9-Trim ethylsilyl-and 9-trimethylgermyl substituted derivatives o f l-(9-fluorenyl)germatranes C i3H 8(R)Ge(OCH2CH2)3N (1 -3) (1: R = H; 2: R = M e3Si; 3: R = M e3Ge) were prepared by the reaction o f 9-tribromogermyl derivatives o f fluorene C i3H8(R)G eBr3 (4 -6) with N(CH2CH20SnAlk3)3 (7: Aik = Et; 8: Aik = Bu). l-(9-Trim ethylstannyl-9-fluorenyl)germatrane (14) was synthesised by the reaction o f the germatrane (1) with M e3SnN M e2. Formulas… Show more
“…[9] Conclusion In summary, metathetical exchange reactions between MHal 4 (M ϭ Ge, Sn; Hal ϭ Cl, Br) and the lithiated parent amines afford compounds 1Ϫ8 in good yields. The presence of a transannular GeǟN interaction in 1 and 3 was confirmed by X-ray diffraction analyses.…”
The reaction between MHal 4 (M = Ge, Sn; Hal = Cl, Br) and N(CH 2 CH 2 NRLi) 3 (R = Me, SiMe 3 ) yields 1-haloazametallatranes 1−8, N(CH 2 CH 2 NR) 3 M−Hal (1, M = Ge, Hal = Cl, R = Me; 2, M = Ge, Hal = Br, R = Me; 3, M = Ge, Hal = Cl, R = SiMe 3 ; 4, M = Ge, Hal = Br, R = SiMe 3 ; 5, M = Sn, Hal = Cl, R = Me; 6, M = Sn, Hal = Br, R = Me; 7, M = Sn, Hal = Cl, R = SiMe 3 ; 8, M = Sn, Hal = Br, R = SiMe 3 ). The composition
“…[9] Conclusion In summary, metathetical exchange reactions between MHal 4 (M ϭ Ge, Sn; Hal ϭ Cl, Br) and the lithiated parent amines afford compounds 1Ϫ8 in good yields. The presence of a transannular GeǟN interaction in 1 and 3 was confirmed by X-ray diffraction analyses.…”
The reaction between MHal 4 (M = Ge, Sn; Hal = Cl, Br) and N(CH 2 CH 2 NRLi) 3 (R = Me, SiMe 3 ) yields 1-haloazametallatranes 1−8, N(CH 2 CH 2 NR) 3 M−Hal (1, M = Ge, Hal = Cl, R = Me; 2, M = Ge, Hal = Br, R = Me; 3, M = Ge, Hal = Cl, R = SiMe 3 ; 4, M = Ge, Hal = Br, R = SiMe 3 ; 5, M = Sn, Hal = Cl, R = Me; 6, M = Sn, Hal = Br, R = Me; 7, M = Sn, Hal = Cl, R = SiMe 3 ; 8, M = Sn, Hal = Br, R = SiMe 3 ). The composition
“…The chemistry of metal derivatives of tripodal ligands such as trialkanolamines, N(CH 2 CHROH) 3 , tris(aminoethyl)amines, N[CH 2 CH 2 N(R)H] 3 , etc., named metallatranes has attracted considerable interest in recent years. − The main focus is the nature of transannular N→M bond, which is strongly affected by the design of the atrane building block and the substituents at the metal atoms. ,− Although a lot of work has appeared on intramolecular nonbonding interactions between nitrogen atoms and atoms of the group 14 and 15 elements and its effect on structural and chemical properties of compounds containing a hypervalent bond, , to the best of our knowledge no atrane types of structure A containing antimony and bismuth as a central atom were structurally characterized and only a few examples were prepared earlier. …”
Syntheses of title compounds, viz. N(CH2CH2NR)3E (1, E = Sb, R = Me; 4, E = Bi, R = Me; 6, E = Sb, R = SiMe3; 8, E = Bi, R = SiMe3), by the reaction of E(NAlk2)3 (3, E = Sb, Alk = Et; 5, E = Bi, Alk = Me) with N(CH2CH2NMeH)3 (2) or N(CH2CH2NSiMe3H)3 (7) are reported. The reactions of SbCl3 with N[CH2CH2N(Me)Li]3 or N[CH2CH2N(SiMe3)Li]3 and BiCl3 with N[CH2CH2N(SiMe3)Li]3 resulted in compounds 1, 6, and 8, respectively. Composition and structures of all novel compounds were established by 1H and 13C NMR spectroscopy and mass spectrometry. The X-ray structural study of 8 clearly indicated the presence of transannular interaction BiNdat in this compound, while 6 possesses a long Sb...Ndat distance. The structural data obtained from geometry optimizations on 6 and 8 reproduce experimental trends, i.e., a decrease in the E-Ndat distance from Sb to Bi. The values of electron density in E-Ndat critical point and the Laplacian of charge density for 8 indicate that a closed-shell interaction exists between the metal atom and Ndat atom.
“…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 of a series of the title compounds, viz., N(CH2CH2NR)3M−X (1, M = Si, X =
Me, R = SiMe3; 2, M = Si, X = Et, R = SiMe3; 3, M = Si, X = n-Bu, R = SiMe3; 4, M = Si,
X = vinyl, R = SiMe3; 5, M = Si, X = Ph, R = SiMe3; 6, M = Ge, X = Me, R = SiMe3; 7, M
= Ge, X = n-Bu, R = SiMe3; 8, M = Ge, X = Ph, R = SiMe3; 9, M = Sn, X = n-Bu, R =
SiMe3; 10, M = Sn, X = Ph, R = SiMe3; 11, M = Si, X = vinyl, R = Me; 12, M = Ge, X = Me,
R = Me) by the reaction of X−MCl3 with N(CH2CH2NSiMe3Li)3 or with N(CH2CH2NMeLi)3
are reported. Reactions of the novel compounds X−Ge(NMe2)3 (15, X = Ph; 16, X =
1-naphthyl; 17, X = 9-antracenyl; 18, X = 9-phenantrenyl) with N(CH2CH2NHMe)3 or N(CH2CH2NH2)3 resulted in new 1-arylazagermatranes, N(CH2CH2NMe)3Ge−X (19, X = Ph; 20,
X = 1-naphthyl; 21, X = 9-antracenyl; 22, X = 9-phenantrenyl) and N(CH2CH2NH)3Ge−X
(23, X = Ph; 24, X = 1-naphthyl; 25, X = 9-phenantrenyl), respectively. 1-Phenylazagermatrane (23) is transformed to 8 by treatment with n-BuLi/Me3SiCl. Composition and
structures of novel compounds were established by elemental analyses, 1H, 13C, and 29Si
NMR spectroscopy, and mass spectrometry. The X-ray structural studies of 10 and 19 clearly
indicated the presence of a transannular interaction M←Nax for both compounds. quasi-Azametallatranes 5 and 8 possess extremely long M←Nax distances.
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