An unsaturated amido-substituted six-vertex germanium cluster and its reactions with alkenes and alkynes

Abstract

The unsaturated metalloid germanium cluster Ge6{N(SiMe3)Dipp}4 2 with two ligand-free germanium atoms and only four amine substituents was obtained starting from the base-coordinated germylene {N(SiMe3)Dipp}GeCl∙DMAP 1 in 50 % yield...

Disproportionation and Ligand Lability in Low Oxidation State Boryl‐Tin Chemistry**

“…Most revealingly (in the context of the tin chemistry outlined above) a combination of multinuclear NMR, micro‐analytical and crystallographic studies shows that this compound is Ge 6 {B(NDippCH) 2 } 4 ( 6 ), i. e. the germanium analogue of Sn 6 {B(NDippCH) 2 } 4 ( 4 ) (Figure 3). [17] Structurally, 4 and 6 are very similar, differing primarily in the E−E and E−B bond lengths, at a level expected based on the differing covalent radii of germanium and tin (Δ r =1.39–1.20=0.19 Å) [18] . The formation of 6 in this way, suggests more broadly that systems of the stoichiometry E 3 {B(NDippCH) 2 } 2 (E = Ge, Sn) are indeed prone to dimerization with accompanying boryl ligand migration.…”

From polygons to polyhedra through intermediate structures. A shape measures study of six-atom inorganic rings and clusters

“…Finally, a couple of compounds 76,77 with 30 valence electrons present a basket shape 16 (E = P, SiR), analogous to those with two more electrons and a single bond for the handle ( 13), and whose purely organic analogue has gone so far unreported. With two less electrons (28), and related to the 30-electron prismatic E 6 R 6 molecules (E = Si-Sn) just discussed, we find the silicon and germanium E 6 R 4 analogues, 78,79 that form an additional E-E bond across the diagonal of a square face, producing a severe loss of the trigonal prismatic shape. In fact, the shapes of those molecules are best described as octahedra distorted toward the edge-bicapped tetrahedron (Fig.…”

Unsaturated amido-substituted six-vertex mixed silicon germanium clusters

“…This bonding situation was also observed in the corresponding clusters E and F, exclusively composed of silicon and germanium, respectively. 25,26 Due to the presence of different mixed silicon germanium clusters in 1-3 further discussion of bond lengths and angles is not possible.…”

“…24 We extended this class of compounds by the highly unsaturated butalene-type analogues Si 6 {N(SiMe 3 )Dipp} 4 E 25 and Ge 6 {N(SiMe 3 )Dipp} 4 F shown in Scheme 1. 26…”