The synthesis and characterization of the tris(1-ethyl-benzoimidazol-2-ylmethyl)amine (BIMEt3 = L) complex of Ge(ii)2+ is described. Oxidation of [LGe]2+ with Selectfluor gives [LGeF2]2+, in a process that is envisaged to involve a tricationic complex [LGeF]3+ as an intermediate, which has been isolated by fluoride ion abstraction from [LGeF2]2+.
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Introducing phospha-bicyclohexene (BCH)-germylenes (BCHGe's) as a novel, multifunctional compound class: the title compounds 15-18 are obtained from simple salt metathesis reactions of dipotassium germacyclopentadienediides K[1] with phosphorusdichlorides. The BCHGe's 15-18 are stabilized by homoconjugation of the germanium(ii) centre with the remote C[double bond, length as m-dash]C double bond. Despite substantial thermodynamic stabilization, phospha-BCHGe's are reactive and undergo a reductive elimination of elemental germanium to give the corresponding phospholes.
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Inorg Chem
January 2024
Chemistry Department, University of Tübingen, Auf der Morgenstelle 18, Tübingen 72076, Germany.
We present the synthesis of alkyl-substituted germylenes GeFlu, Ge(Flu), and FluGeCl (Flu = 9-fluorenyl, Flu = 9-trimethylsilyl-9-fluorenyl) using bulky fluorenyl ring systems and modifications of that. GeFlu can only be crystallized as its three-membered ring trimer, whereby the reaction is accompanied by the formation of several byproducts, such as [Li(THF)][Ge(GeFluH)]. These results led to the modification of the fluorenyl framework by substitution the one H atom in the 9-position by a TMS group.
View Article and Find Full Text PDFActivation of Protic, Hydridic and Apolar E-H Bonds by a Boryl-Substituted Ge Cation.
Chemistry
January 2020
Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK.
The synthesis of a boryl-substituted germanium(II) cation, [Ge{B(NDippCH) }(IPrMe)] , (Dipp=2,6-diisopropylphenyl) featuring a supporting N-heterocyclic carbene (NHC) donor, has been explored through chloride abstraction from the corresponding (boryl)(NHC)GeCl precursor. Crystallographic studies in the solid state and UV/Vis spectra in fluorobenzene solution show that this species dimerizes under such conditions to give [(IPrMe){(HCNDipp) B}Ge=Ge{B(NDippCH) }(IPrMe)] (IPrMe = 1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene), which can be viewed as an imidazolium-functionalized digermene. The dimer is cleaved in the presence of donor solvents such as [D ]thf or [D ]pyridine, to give monomeric adducts of the type [Ge{B(NDippCH) }(IPrMe)(L)] .
View Article and Find Full Text PDFOxidation of a germanium(ii) dication to access cationic germanium(iv) fluorides.
Chem Commun (Camb)
April 2018
Department of Chemistry, University of Victoria, Victoria, British Columbia V8W 3V6, Canada.
The synthesis and characterization of the tris(1-ethyl-benzoimidazol-2-ylmethyl)amine (BIMEt3 = L) complex of Ge(ii)2+ is described. Oxidation of [LGe]2+ with Selectfluor gives [LGeF2]2+, in a process that is envisaged to involve a tricationic complex [LGeF]3+ as an intermediate, which has been isolated by fluoride ion abstraction from [LGeF2]2+.
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Acc Chem Res
August 2017
Technische Universität Berlin, Department of Chemistry, Metalorganics and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, 10623 Berlin, Germany.
Monoatomic zerovalent main-group element complexes emerged very recently and attracted increasing attention of both theoretical and experimental chemists. In particular, zerovalent silicon complexes and their congeners (metallylones) stabilized by neutral Lewis donors are of significant importance not only because of their intriguing electronic structure but also because they can serve as useful building blocks for novel chemical species. Featuring four valence electrons as two lone pairs at the central atoms, such complexes may form donor-acceptor adducts with Lewis acids.
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