Oxidation of germa- and stanna-closo-dodecaborate

Abstract

The oxidation of closo-heteroborates [GeB11H11](2-) and [SnB11H11](2-) is presented. Upon oxidation germa-closo-dodecaborate yields a symmetrical dimer exhibiting a Ge-Ge bond between two clusters. This dimer shows sulphur insertion into the Ge-Ge bond at room temperature. In contrast, oxidation of the homologous tin cluster results in an unsymmetrical dimer bearing an Sn-B bond between two clusters. The Sn-B dimer is also the product of the hydride abstraction reaction. In the presence of the donor ligand 2,2'-bipyridine, the oxidation of closo-cluster [SnB11H11](2-) leads to the Sn(IV)-half sandwich coordination compound [bipy-SnB11H11] which dissolves in DMSO to give the Sn(IV)-adduct [bipy(DMSO)-SnB11H11].

Boranyl‐Functionalized [Ge9] Clusters: Providing the Idea of Intramolecular Ge/B Frustrated Lewis Pairs

“…[2,30] The DAB ligands in 2 a-Cu and 3 a-Cu bind to the [Ge 9 ] cluster through exo-cluster single bonds between one cluster vertex atom and the B atom, with GeÀB distances of 2.063(5) and 2.055 (5) , respectively. The bond lengths are in the range of previously reported GeÀB bonds in germaborates, [31] germacarboranes [32] or germylenes. [25, 26b,c,e, 33] The [NHC Dipp Cu] + fragment coordinates one of the trigonal bases of the prism in an h 3 -fashion with Ge-Cu distances known for analogous complexes.…”

Boranyl‐Functionalized [Ge9] Clusters: Providing the Idea of Intramolecular Ge/B Frustrated Lewis Pairs

“…[2,30] The DAB ligands in 2 a-Cu and 3 a-Cu bind to the [Ge 9 ] cluster through exo-cluster single bonds between one cluster vertex atom and the B atom, with GeÀB distances of 2.063(5) and 2.055(5) , respectively. The bond lengths are in the range of previously reported GeÀB bonds in germaborates, [31] germacarboranes [32] or germylenes. [25, 26b,c,e, 33] The [NHC Dipp Cu] + fragment coordinates one of the trigonal bases of the prism in an h 3 -fashion with Ge-Cu distances known for analogous complexes.…”

Impact scenarios in boron carbide: A computational study

“…However, it is important to consider other experimental evidence regarding the mechanism behind the extraordinary resistance to radiation of icosahedral-boron solids; alongside boron carbide there are several examples of materials that contain icosahedral boron structures, with other atoms occupying chain positions, such as boron phosphide 8 , arsenide 9 and oxide 10 . There are also several examples of heterosubstituted icosahedra with elements as varied as technetium 33 , tin or germanium at the icosahedral vertices 34 . It is feasible then, that the stabilisation of damaged icosahedra by the abstraction of a chain atom of a different element would be a viable mechanism to resistance of these solids to radiation.…”