Synthesis and Characterisation of 1-[9-(H, Me3Si, Me3Ge, Me3Sn)9-Fluorenyl]-3,7,10-trimethylgermatranes. The Crystal Structure Analysis of 1-(9-Fluorenyl)-3,7,10-trimethylgermatrane
“…In contrast to compound 5, the carbon atoms lying in the -positions to the N atom occupy flap sites, while the C-␣ atoms are part of the base of the envelope planes. This seems to be characteristic for the structures of 3,7,10-trimethyl-substituted atranes [44,45,[47][48][49]. The carbon atoms of atrane cage in the -positions to the N atom are disordered between two opposite flap sites in the structures of 2, Z-15, and 25.…”
Section: Crystal Structures Of 2 5 Z-15 Z-22 and 25mentioning
“…In contrast to compound 5, the carbon atoms lying in the -positions to the N atom occupy flap sites, while the C-␣ atoms are part of the base of the envelope planes. This seems to be characteristic for the structures of 3,7,10-trimethyl-substituted atranes [44,45,[47][48][49]. The carbon atoms of atrane cage in the -positions to the N atom are disordered between two opposite flap sites in the structures of 2, Z-15, and 25.…”
Section: Crystal Structures Of 2 5 Z-15 Z-22 and 25mentioning
“…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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