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Synthesis, structure and reactivity of terphenyl-substituted germylium-ylidene cations
- Source :
- Polyhedron. 196:115006
- Publication Year :
- 2021
- Publisher :
- Elsevier BV, 2021.
-
Abstract
- The first examples of isolable two-coordinate terphenyl-substituted germylium-ylidenes are reported. These systems, of composition [(NHC)(Ar)Ge]+, exploit a range of aryl and NHC substituents (ArMes, ArTrip; IMe4, IPrMe) and are isolated by employing weakly coordinating borate or aluminate counter-ions. The use of the smallest combination of substituents used in this study (IMe4 and ArMes) results in the formation of a dicationic dimer, [(IMe4)(ArMes)Ge=Ge(ArMes)(IMe4)]2+, which can also be viewed as an imidazolium-functionalized digermene. Increasing the steric loading (at either the NHC or terphenyl ligand) leads to the formation of the monomeric germylium-ylidene cations [(IMe4)(ArTrip)Ge]+, [(IPrMe)(ArMes)Ge]+, and [(IPrMe)(ArTrip)Ge]+, stabilized in the solid state to varying degrees by secondary interactions with the peripheral arene π systems or C–H bonds. These three systems are characterized by widening C–Ge–C angles (101.7(1), 105.0(2) and 107.2(1)°, respectively) as the steric profiles of the germanium-bound substituents increase. In the case of dication [(IMe4)(ArMes)Ge=Ge(ArMes)(IMe4)]2+, its ability to act as a functional source of the corresponding monomeric germylium-ylidene, [(IMe4)(ArMes)Ge]+, is demonstrated through its reaction with PhSiH3 in bromobenzene solution, which generates the monomeric GeIV species [(IMe4)(ArMes)Ge(H)(SiH2Ph)]+ via Si–H oxidative addition at germanium.
- Subjects :
- Steric effects
010405 organic chemistry
Ligand
Aryl
Dimer
010402 general chemistry
01 natural sciences
Oxidative addition
0104 chemical sciences
Dication
Inorganic Chemistry
chemistry.chemical_compound
Crystallography
chemistry
Terphenyl
Materials Chemistry
Reactivity (chemistry)
Physical and Theoretical Chemistry
Subjects
Details
- ISSN :
- 02775387
- Volume :
- 196
- Database :
- OpenAIRE
- Journal :
- Polyhedron
- Accession number :
- edsair.doi...........eac79ace895047aa23dd538c3c480787