title: Synthesis and characterization of the first azastibatranes and azabismatranes.
abstract: 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.
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, D-35032 Marburg/Lahn, Germany.
authors.forename: Pavel L
authors.initials: PL
authors.lastname: Shutov
authors.forename: Sergey S
authors.initials: SS
authors.lastname: Karlov
authors.forename: Klaus
authors.initials: K
authors.lastname: Harms
authors.forename: Daniil A
authors.initials: DA
authors.lastname: Tyurin
authors.forename: Andrei V
authors.initials: AV
authors.lastname: Churakov
authors.forename: Jörg
authors.initials: J
authors.lastname: Lorberth
authors.forename: Galina S
authors.initials: GS
authors.lastname: Zaitseva