“Splendid Isolation” eines Nichtmetalldikations

Abstract

Eingesperrt, aber glücklich: Das Triflatsalz eines Germanium(II)‐Dikations – eines atomaren Nichtmetallkations also – konnte isoliert werden, indem das Germanium(II)‐Ion im [2.2.2]Cryptanden eingekapselt wurde (gezeigt sind die Strukturformel (links) sowie die Molekülstruktur im Kristall (Mitte: Kugel‐Stab‐Modell, rechts: Kalottenmodell)). Der Cryptand befriedigt den Elektronenbedarf des Kations und schirmt es sterisch ab.

A Novel Soluble InI Precursor for Pn Ligand Coordination Chemistry

“…Furthermore, In I compounds have proved to be valuable catalysts in organic synthesis 2. Recently, the preparation and stabilization of monocationic3 and polycationic4 species became of great interest and represent very active areas of research. Thereby, the balance between the stabilization and the occurrence of a high reactivity is a general goal.…”

“…However, the topological analysis of the electron density [25] does not indicate a bond critical point between In1 and In1' (see the Supporting Information). Compared to 10, significantly shorter InÀIn distances (2.887(2)-3.18(2) ) are found in tetrahedral In 4 clusters synthesized in the groups of Uhl, Cowley, and Linti, which definitely show In I À In I interactions. [1a,g, 26] Even shorter In À In distances (2.696 (2) ) are reported for a trigonalplanar In 4 cluster by Power et al [27] However, in the compounds [InC 5 R 5 ] (R= H, Me) the intermetallic distances (3.942(1)-3.986(1) ) are considerably longer than those in 10.…”

“…Thus, the first coordination compounds of P n -ligand complexes with indium have been prepared. With compound 10 containing the [Cp 2 Mo 2 (CO) 4 -A C H T U N G T R E N N U N G (m,h 2 -P 2 )] ligand an unprecedented tetrametallic aggregate has been synthesized, which features a short In···In distance. Moreover, the coordination of a cyclo-P 3 ligand to a main group metal as present in 12 is unique and reveals a novel coordination mode of a cyclo-P 3 unit.…”