The isolation and characterization of the first silicon analogue of the aromatic cyclobutadiene dication is reported. The aromatic 2π-electron tetrasilacyclobutadiene dication in [(Si)](BPh) ( = PhC(NBu)) has been obtained in a simple and straightforward synthesis, from [SiCl], [SiSi] and NaBPh, and fully characterized. The molecular structure reveals a four-membered Si-dication in an almost perfect square-planar geometry. Theoretical calculations support the interpretation of the title compound as a classical 2π-aromatic species with a singlet ground state.
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A Stable Aromatic Tetrasilacyclobutadiene Dication.
J Am Chem Soc
September 2019
Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT) , Engesserstrasse 15 , 76131 Karlsruhe , Germany.
The isolation and characterization of the first silicon analogue of the aromatic cyclobutadiene dication is reported. The aromatic 2π-electron tetrasilacyclobutadiene dication in [(Si)](BPh) ( = PhC(NBu)) has been obtained in a simple and straightforward synthesis, from [SiCl], [SiSi] and NaBPh, and fully characterized. The molecular structure reveals a four-membered Si-dication in an almost perfect square-planar geometry.
View Article and Find Full Text PDFSilicon-containing formal 4π-electron four-membered ring systems: antiaromatic, aromatic, or nonaromatic?
Chemistry
June 2012
Lab of Computational Chemistry and Drug Design, Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055, PR China.
Density functional theory calculations (B3LYP) have been carried out to investigate the 4π-electron systems of 2,4-disila-1,3-diphosphacyclobutadiene (compound 1) and the tetrasilacyclobutadiene dication (compound 2). The calculated nucleus-independent chemical shift (NICS) values for these two compounds are negative, which indicates that the core rings of compounds 1 and 2 have a certain amount of aromaticity. However, deep electronic analysis reveals that neither of these two formal 4π-electron four-membered ring systems is aromatic.
View Article and Find Full Text PDFFormation of a donor-stabilized tetrasilacyclobutadiene dication by a Lewis acid assisted reaction of an N-heterocyclic chloro silylene.
J Am Chem Soc
June 2011
Institute of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17, Juni 135, Sekr. C2, D-10623 Berlin, Germany.
The first donor-stabilized tetrasilacyclobutadiene dication species has been synthesized and fully characterized. Its unexpected formation occurs by the Lewis acid assisted reaction of the N-heterocyclic chloro silylene [L(Si:)Cl] (L = PhC(NtBu)(2); amidinate) with Cp*ZrCl(3) (Cp* = pentamethylcyclopentadienyl) in the molar ratio of 3:2. Remarkably, the four-membered Si(4) core consists of two N-donor stabilized silylium subunits and two silylene-like moieties.
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