The first isolable molecular silicon dicarbonate complex (bis-NHC)Si(CO ) 2 (bis-NHC=H C[{NC(H)=C(H)N(Dipp)}C:] , Dipp=2,6-iPr C H ) was synthesized by facile reaction of the bis-N-heterocyclic carbene stabilized silylone (bis-NHC)Si 1, bearing a zero-valent silicon atom, with carbon dioxide. The monomeric silicon dioxide complex (bis-NHC)SiO 3 supported by the bis-NHC ligand was proposed as a key intermediate resulting from double oxygenation of the zero-valent silicon atom in 1 by two molar equivalents of CO under liberation of CO; its subsequent Lewis acid-base reaction with CO leads to 2 which has been fully characterized including an single-crystal X-ray diffraction analysis. Its electronic structure, spectroscopic data and the thermochemistry of the formation have been studied quantum-chemically.
The synthesis of the unprecedented monomeric Si selenide complex (bis-NHC)Si=Se→GaCl 2 (bis-NHC=bis-N heterocyclic carbene, H C[{NC(H)=C(H)N(Dipp)}C:] , Dipp=2,6-iPr C H ), bearing the elusive SiSe ligand as a heavy CO homologue by the reaction of the silylone-GaCl adduct (bis-NHC)Si→GaCl 1 with elemental selenium in acetonitrile, is reported. The similar conversion of 1 with excess selenium conducted in THF afforded the SiSe complex (bis-NHC)Si(=Se)Se→GaCl 3. Remarkably, the reaction of 1 with Te=P(nBu) as a gentle Te transfer reagent led to the isolation of the monomeric SiTe complex (bis-NHC)SiTe 4, the first structurally characterized Lewis acid free heavy CO homologue 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.
The synthesis of the unprecedented monomeric Si II selenide complex (bis-NHC)Si=Se!GaCl 3 2 (bis-NHC = bis-Nh eterocyclic carbene,H 2 C[{NC(H)=C(H)N(Dipp)}CD] 2 , Dipp = 2,6-iPr 2 C 6 H 3 ), bearing the elusive SiSe ligand as ah eavy CO homologue by the reaction of the silylone-GaCl 3 adduct (bis-NHC)Si!GaCl 3 1 with elemental selenium in acetonitrile,isreported. The similar conversion of 1 with excess selenium conducted in THF afforded the SiSe 2 complex (bis-NHC)Si(=Se)Se!GaCl 3 3.Remarkably,the reaction of 1 with Te=P(nBu) 3 as agentle Te transfer reagent led to the isolation of the monomeric SiTe 2 complex (bis-NHC)SiTe 2 4,t he first structurally characterized Lewis acid free heavy CO 2 homologue complex. The isolated compounds 2, 3,and 4 have been fully characterized,i ncluding single-crystal X-ray diffraction analyses.T heir electronic structures and spectroscopic data have also been studied by quantum-chemical calculations.Carbonmonoxide,CO, featuring amonomeric structure and Angewandte Chemie Communications 6299
The first isolable molecular silicon dicarbonate complex (bis-NHC)Si(CO 3 ) 2 2 (bis-NHC = H 2 C[{NC(H) = C-(H)N(Dipp)}CD] 2 ,D ipp = 2,6-iPr 2 C 6 H 3 )w as synthesized by facile reaction of the bis-N-heterocyclic carbene stabilized silylone (bis-NHC)Si 1,b earing az ero-valent silicon atom, with carbon dioxide.T he monomeric silicon dioxide complex (bis-NHC)SiO 2 3 supported by the bis-NHC ligand was proposed as akey intermediate resulting from double oxygenation of the zero-valent silicon atom in 1 by two molar equivalents of CO 2 under liberation of CO;i ts subsequent Lewis acid-base reaction with CO 2 leads to 2 whichh as been fully characterized including an single-crystal X-ray diffraction analysis.I ts electronic structure,s pectroscopic data and the thermochemistry of the formation have been studied quantumchemically.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.
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