title: Taming Silicon Congeners of CO and CO2: Synthesis of Monomeric SiIIand SiIVChalcogenide Complexes.
abstract: The synthesis of the unprecedented monomeric SiIIselenide complex (bis-NHC)Si=Se→GaCl32 (bis-NHC=bis-N heterocyclic carbene, H2C[{NC(H)=C(H)N(Dipp)}C:]2, Dipp=2,6-iPr2C6H3), bearing the elusive SiSe ligand as a heavy CO homologue by the reaction of the silylone-GaCl3adduct (bis-NHC)Si→GaCl31 with elemental selenium in acetonitrile, is reported. The similar conversion of 1 with excess selenium conducted in THF afforded the SiSe2complex (bis-NHC)Si(=Se)Se→GaCl33. Remarkably, the reaction of 1 with Te=P(nBu)3as a gentle Te transfer reagent led to the isolation of the monomeric SiTe2complex (bis-NHC)SiTe24, the first structurally characterized Lewis acid free heavy CO2homologue complex. The isolated compounds 2, 3, and 4 have been fully characterized, including single-crystal X-ray diffraction analyses. Their electronic structures and spectroscopic data have also been studied by quantum-chemical calculations.
authors.affiliation: Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
authors.forename: Alexander
authors.initials: A
authors.lastname: Burchert
authors.affiliation: Technische Universität Berlin, Department of Chemistry: Theoretical Chemistry/Quantum Chemistry, Sekr. C7, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Robert
authors.initials: R
authors.lastname: Müller
authors.affiliation: Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
authors.forename: Shenglai
authors.initials: S
authors.lastname: Yao
authors.affiliation: Technische Universität Berlin, Department of Chemistry: Theoretical Chemistry/Quantum Chemistry, Sekr. C7, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Caspar
authors.initials: C
authors.lastname: Schattenberg
authors.affiliation: Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
authors.forename: Yun
authors.initials: Y
authors.lastname: Xiong
authors.affiliation: Technische Universität Berlin, Department of Chemistry: Theoretical Chemistry/Quantum Chemistry, Sekr. C7, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Kaupp
authors.affiliation: Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
authors.forename: Matthias
authors.identifier: 0000-0002-9873-4103
authors.initials: M
authors.lastname: Driess
keywords: main-group chemistry; multiple bonds; silica analogues; silicon; silylone