Synthesis of a germanium analogue of a dithiocarboxylic acid anhydride from the Ge(i) pyridyl-1-azaallyl dimer

Abstract

The reaction of pyridyl-1-azaallyl germanium(ii) chloride RGeCl () [R = {N(SiMe(3))C(Ph)C(SiMe(3))(C(5)H(4)N-2)}] with lithium metal afforded the dimeric germanium(i) compound [(RGe)(2)] (); compound reacts with an excess of elemental sulfur to afford the novel germanium analogue of a dithiocarboxylic acid anhydride [{Ge(S)R}(2)S] () via the insertion of elemental sulfur into the Ge(i)-Ge(i) bond followed by the oxidative-addition of elemental sulfur to the germanium(ii) centres.

Heavier Group 13 Metal(I) Heterocycles Stabilized by Sterically Demanding Diiminophosphinates: A Structurally Characterized Monomer–Dimer Pair For Gallium

“…The unusualr eactivity of terphenylg allium(I) speciesi sm ainly facilitated by their dimers (ArGaGaAr) that can, for example, activate alkenes via lower barriers compared with their monomers because of matching frontier orbitals of correctsymmetry. [21] In addition to clear relations to other dimericG roup 13 metal(I)compounds, the set of bonding orbitals in the calculated dimer molecules [( Dip LE) 2 ]c ompares very well with those of related Group 14 element(I) speciesL EEL, in which E = Si, Ge, Sn andP b, and L = as terically demandinga midinateo rg uanidinate ligand, [31,32] albeit with ad ifferent level of orbital occupation. With N,N'-chelating ligandss uch as amidinates and guanidinates,t he Group 14 element species contain EÀE single-bonds and elementlone pair contributions.…”

“…Thus, this bonding situation is comparable to that of alkene analogues of heavierG roup 14 elementc ompounds [2] and the orbital overlap furthermore showss imilarities to dimeric Group 14 element(I) compounds with N,N'-chelating ligands. [31,32]…”

A Comprehensive Investigation of a Zwitterionic GeI Dimer with a 1,2‐Dicationic Core

“…The Ge−Ge bond distance in 1Ge (2.5687(9) Å) is short relative to reported dimeric Ge I compounds featuring monoanionic ligands (2.569(5)–2.6380(8) Å), and is comparable to the only other reported example of a phosphine‐supported Ge 1,2‐dicationic core ( F , 2.540(1) Å) . 1,2‐Dications are known to have short E−E bonds despite the Coulombic repulsion, a phenomenon linked to the electronic structure of the compound .…”

Oxidation of germa- and stanna-closo-dodecaborate

“…2 3)°. [30][31][32][33][34] In analogy to the oxidation of the germanium cluster 1 the reaction of the homologous tin cluster [SnB 11 H 11 ] 2− with the ferrocenium salt [Cp 2 Fe][PF 6 ] was also investigated. To our The 119 Sn{ 1 H} NMR spectrum of 5 shows two characteristic signals at −267 [q] and −558 [s] ppm respectively.…”