Breaking the molecular symmetry by protonation of germylene 1 is the key step in the synthesis of the germyliumylidene 2, which is stabilized by an intramolecular interaction with a distant imido group.
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Heterobimetallic Hydrides with a Germanium(II)-Zinc Bond.
Chemistry
September 2023
Institute for Inorganic Chemistry, RWTH Aachen University, 52056, Aachen, Germany.
In the presence of TMEDA (TMEDA=N,N,N',N'-tetramethylethylenediamine), zinc dihydride reacted with germanium(II) compounds (BDI-H)Ge (1) and [(BDI)Ge][B(3,5-(CF ) C H ) ] (3) (BDI-H = HC{(C=CH )(CMe)(NAr) }, BDI = [HC(CMeNAr) ]; Ar = 2,6- Pr C H ) by formal insertion of the germanium(II) center into the Zn-H bond of polymeric [ZnH ] to give neutral and cationic zincagermane with a H-Ge-Zn-H core [(BDI-H)Ge(H)-(H)Zn(tmeda)] (2) and [(BDI)Ge(H)-(H)Zn(tmeda)][B(3,5-(CF ) C H ) ] (4), respectively. Compound 2 eliminated [ZnH ] giving diamido germylene 1 at 60 °C. Compound 2 and deuterated analogue 2-d exchanged with [ZnH ] and [ZnD ] in the presence of TMEDA to give a mixture of 2 and 2-d .
View Article and Find Full Text PDFStructural Influence of Lone Pairs in GeP N , a Germanium(II) Nitridophosphate.
Angew Chem Int Ed Engl
January 2023
Department of Chemistry, Ludwig-Maximilians-University Munich, Butenandtstraße 5-13, 81377, Munich, Germany.
Owing to their widespread properties, nitridophosphates are of high interest in current research. Explorative high-pressure high-temperature investigations yielded various compounds with stoichiometry MP N (M=Be, Ca, Sr, Ba, Mn, Cd), which are discussed as ultra-hard or luminescent materials, when doped with Eu . Herein, we report the first germanium nitridophosphate, GeP N , synthesized from Ge N and P N at 6 GPa and 800 °C.
View Article and Find Full Text PDFA "Push-Pull" Stabilized Phosphinidene Supported by a Phosphine-Functionalized β-Diketiminato Ligand.
Chemistry
July 2020
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, UK.
The use of a bis(diphenyl)phosphine functionalized β-diketiminato ligand, [HC{(CH )C} {(ortho-[P(C H ) ] C H )N} ] (PNac), as a support for germanium(II) and tin(II) chloride and phosphaketene compounds, is described. The conformational flexibility and hemilability of this unique ligand provide a versatile coordination environment that can accommodate the electronic needs of the ligated elements. For example, chloride abstraction from [(PNac)ECl] (E=Ge, Sn) affords the cationic germyliumylidene and stannyliumylidene species [(PNac)E] in which the pendant phosphine arms associate more strongly with the Lewis acidic main group element centers, providing further electronic stabilization.
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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