Antimony tris‐amides — (Et2N)3−nSb[N(C6F5)(2‐C5H4N)]n [n = 1 (3), 2 (4) or 3 (5)] — have been prepared by treatment of Sb(NEt2)3 (1) with stoichiometric amounts of (2‐C5H4N)(C6F5)NH (2). In contrast to amide 5, compounds 3 and 4 are unexpectedly unstable and react further to give the bis‐amido antimony fluorides [(2‐Et2N‐C6F4)(2‐C5H4N)N]Sb(F)[N(C2H5)2] (6) and [(2‐Et2N‐C6F4)(2‐C5H4N)N]Sb(F)[N(C6F5)(2‐C5H4N)] (7). The structure of 7 was confirmed by X‐ray diffraction studies. DFT calculations, which reproduce the principal features of compound 7’s geometry, have been used to explain the possible reaction pathway of this ortho‐directed metathetical fluoride‐amide exchange. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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.

Germanium, Azagermatranes The reaction of tris(dimethylamino)halogermanes, (Me?N)3GeHal (7, Hal = Cl; 8 , Hal = Br), with tris(2-aminoethyl)amines, N(CH2CH2NHR)3 (5, R = H; 6 , R = Me), yield l-halo-N,N',N"-azagermatranes (1, X = Cl, R = H; 2, X = Br, R = H; 3, X = Cl, R = Me; 4, X = Br, R = Me). Treatment of 4 with n-butyllithium affords l-n-butyl-N,N',N"-trimethylazagermatrane (14) in high yield. Reactions of n-BuLi with 7 or (Me2N)4Ge (13) lead to the formation of (Me2N)3Ge-n-Bu (15). On treatment of 15 with 5 the 1 -n-butylazagermatrane 16 was obtained. The molecular composition and the structures of all new compounds were established by elemental analyses, 'H and 13C NMR spectroscopy and mass spectrometry.

The title compound, viz. (C 6 F 5 ) 2 NLi was prepared as dimeric complexes with Et 2 O or THF by the reaction of (C 6 F 5 ) 2 NH (DFDPA) with n-BuLi. Identity and structures were established by elemental analyses, 1 H, 13 C, and 19 F NMR spectroscopy, and IR spectroscopy. The crystal structures of dimeric [(C 6 F 5 ) 2 NLi(Et 2 O)] 2 Lithium Bis(pentafluorphenyl)amid ؊ Synthese und strukturelle Charakterisierung der Komplexe mit Diethylether und THF Inhaltsübersicht. Die Titelverbindung, (C 6 F 5 ) 2 NLi, wurde in Form dimerer Komplexe mit Et 2 O oder THF durch Reaktion von (C 6 F 5 ) 2 NH (DFDPA) mit n-BuLi erhalten. Die Charakterisierung erfolgte über Elementaranalyse, 1 H-, 13 C-, und 19 F-NMR