Synthesis and Characterization of Group 14 1-Haloazametallatranes

Abstract

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

Synthesis and structural consideration of 1‐chloro‐N,N′,N″‐tris(pentafluorophenyl)azagermatrane: Azagermatrane with the shortest intramolecular N → Ge bond

“…However, in contrast to the correlation predicted by 3c-4e bond theory (see above) [9], the elongation of Ge←N ax bond length in studied 1-chloroazagermatranes: 1, 2.148(7)Å < N(CH 2 CH 2 NMe) 3 GeCl, 2.167(4)Å < N(CH 2 CH 2 NSiMe 3 ) 3 GeCl, 2.278(2)Å does not correlate with the shortening of Ge Cl bond distances in the same compounds: N(CH 2 CH 2 NMe) 3 also do not meet the expectations. The Ge N eq bond lengths in 1 is close to those previously found in N(CH 2 CH 2 NSiMe 3 ) 3 GeCl, 1.838(2)Å and N(CH 2 CH 2 NMe) 3 GeCl, 1.858(2)Å [4], but the analysis of these data is difficult due to the direct influence of the nature of substituents R on these values.…”

“…Their aza-analogs, azagermatranes, N(CH 2 CH 2 NR) 3 Ge X, are less studied. The common coordination polyhedron of Ge atom in these compounds is trigonal bipyramid (TBP) with N and X in axial positions and O (or NR) in equatorial sites [4,5].…”

Novel derivatives of hypervalent germanium: synthesis, structure, and stability

“…As a part of our investigation program to study the complexes of main group elements as well as transition metals with Y(CH 2 CH 2 Z) 2 2-and N(CH 2 CH 2 Z) 3 3ligands (Y = AlkN, ArN; Z = O, NSiMe 3 , NAlk), [20][21][22][23][24][25][26][27][28][29][30] we report herein the synthesis and crystal structures of the first examples of germanium complexes based on diethylenetriamine type ligands-1,3,6,2-triazagermocanes or "azagermocanes". An unusual intramolecular dehalosilylation process was found and discussed.…”

“…Displacement ellipsoids are shown at the 50% probability level.This conclusion is supported by X-ray data obtained early for three azagermatranes. The N(ax)→Ge bond distances in these compounds vary in broad interval due to varying of the equatorial groups at Ge atom: N(CH 2 CH 2 N 6 F 5 ) 3 GeCl (2.148(7) A ˚), 31 N(CH 2 CH 2 NMe) 3 Ge-Cl (2.167(4) A ˚), N(CH 2 CH 2 NSiMe 3 ) 3 GeCl (2.278(2) A ˚) 20. The coordination polyhedron of the N(eq) atoms in compounds 1-4 is a slightly distorted trigonal plane while the environment of the N(ax) atoms is approximately tetrahedral.…”

The transannular interaction germanium–nitrogen in germocanes: The influence of substituents

“…In continuation of our investigations in the chemistry of metallatranes [39][40][41][42][43][44] and metallocanes [28] we focused our efforts on the synthesis and characterization of germocanes bearing various substituents at the Ge and N atoms, as well as at the carbon atoms of ocane skeleton. It should be noted that the latter compounds with substituents at C atoms are almost unexplored to date.…”