Group 13 Azatranes: Synthetic, Conformational, and Configurational Features.

PINKAS, Jiří, B. GAUL and J. G. VERKADE. Group 13 Azatranes: Synthetic, Conformational, and Configurational Features. Journal of the American Chemical Society. Washington, D.C.: American Chemical Society, 1993, vol. 115, No 10, p. 3925-3931. ISSN 0002-7863.

Basic information

Original name

Group 13 Azatranes: Synthetic, Conformational, and Configurational Features.

Authors

PINKAS, Jiří, B. GAUL and J. G. VERKADE

Edition

Journal of the American Chemical Society, Washington, D.C. American Chemical Society, 1993, 0002-7863

---

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10402 Inorganic and nuclear chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

Organization unit

Faculty of Science

Keywords in English

AZASILATRANES; NITROGEN

Tags

AZASILATRANES, Nitrogen

---

Abstract

V originále

The monomeric azatranes E(RNCH2CH2)3N 7 (E = B, R = Me), 8 (E = B, R = SiMe3), and 9 (E = Al, R = SiMe3) can be synthesized from E(NMe2)3 and (HRNCH2CH2)3N in low yields (6-37%). The azatrane 10 (E = Al, R = Me), formed in 64% yield by the analogous reaction, is a stable dimer featuring a four-membered MeNAlNMeAl ring in which the aluminum is five-coordinate as shown by H-1, C-13, and Al-27 NMR spectroscopic techniques (including two-dimensional ones). Compound 7 can be made in 30% yield by reacting 10 with B(OMe)3. Compound 8, in contrast to 7 and 9, exists as rigid enantiomers that interconvert slowly at room temperature on the NMR time scale owing to steric repulsion of the Me3Si groups. VT H-1 and B-11 NMR studies provide evidence for a concerted (rather than a stepwise) racemization mechanism (DELTAH(double dagger), 61 +/- 5 kJ.mol-1; DELTAS(double dagger), -36 +/- 13 J.mol-1 K-1) involving a symmetric (C3v) transition state that retains the transannular bond.