Metalloid Cluster Compounds of Germanium: Synthesis – Properties – Subsequent Reactions

Abstract

Keywords: Germanium / Metalloid clusters / Metals / IntermediatesMetalloid cluster compounds represent ideal model compounds that provide an insight into the area between the molecular and the solid state. This borderland is of particular interest especially for metals or semimetals, as a drastic change of the physical properties takes place from the oxidized species (salt, nonconducting) to the bulk phase (metal, semimetal, conducting, semiconducting).

Sn(I) halides: Novel binary compounds of tin and their application in synthetic chemistry

“…However, in the case of 1, the polyhedron is empty. Additionally the 14 germanium atoms in (THF) 6 Li 3 Ge 14 [Ge(SiMe 3 ) 3 ] 5 2 [8] form an empty polyhedron (Fig. 1), showing that larger empty polyhedrons are even stable for the higher congeners of carbon hinting to a possible route to ''germa-fullerenes".…”

“…During the last years metalloid cluster compounds of germanium of the general formulae Ge n R m (n > m) could be established as a novel group of substances [5]. Thereby we have been able to establish a fruitful synthetic route via the disproportionation reaction of a metastable Ge(I) halide (GeBr or GeCl), leading to cluster compounds with up to 14 germanium atoms in the cluster core [6]. The structural characterization of the so far synthesized compounds reveals that novel structural motives can be realized on the way to the bulk phase of elemental germanium.…”

Germa‐closo‐dodecaborate: A New Ligand in Transition‐Metal Chemistry with a Strong trans Influence

“…[12] Crystallography: X-ray data for compounds 2-5 were collected with a Stoe IPDS 2T diffractometer and corrected for Lorentz and polarisation effects and absorption by air. The programs used in this work were Stoes's X-Area [36] and WinGX suite of programs [37] including SHELXS [38] and SHELXL [39] for structure solution and refinement.…”

“…[10] Besides the classical coordination chemistry of germanium ligands the long known Zintl anions and metalloid cluster compounds of germanium have returned into focus. [11,12] We are interested in the coordination chemistry of group IV heteroborates. The syntheses of homologues of the monoA C H T U N G T R E N N U N G carbaborate anion [1ÀXB 11 H 11 ] 2À (X = Ge, Sn, Pb) was reported for the first time in 1992 by Todd and co-workers.…”

Reactions of exo‐Substituted RSn93− Clusters with Pd: Endohedral Cluster Formation and Oxidative Insertion

“…These compounds represent a link between the alkylated Group 14 "metalloid" clusters and the more traditional Zintl ions. [26][27][28][29][30][31][32] In particular, the [ 3À clusters, wherein R is an exo-bonded alkyl or posttransition metal group, have been prepared by nucleophilic substitution reactions. [33][34][35][36][37][38] Unlike the multicenter two-electron bonding within the E 9 clusters, the exo substituents are attached to the clusters through two-center, two-electron bonds.…”