SO2 Activation by the Bis(guanidinato)silylene [iPrNC(NiPr2)NiPr]2Si: Formation of Neutral Six‐Coordinate Silicon(IV) Complexes with a Chelating Sulfito or Dithionito Ligand

Mück, Felix M.; Baus, Johannes A.; Bertermann, Rüdiger; Tacke, Reinhold

doi:10.1002/ejic.201600294

Cited by 8 publications

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“…2,20−22 Amine derivatives are employed for this purpose. 21 Presently, frustrated Lewis pairs, 20,23 phosphine derivatives, 24,25 ionic liquids, 11,26−29 metal−organic frameworks, 30−33 and silylene complexes 22,34 are the front runners of SO 2 sequestering agents.…”

Section: Introductionmentioning

confidence: 99%

Schematic Design of Metal-Free NHC-Mediated Sequestering and Complete Conversion of SO₂ to Thiocarbonyl S-Oxide Derivatives at Room Temperature

2022

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The sequestering and complete conversion of SO 2 to valuable chemicals in a metal-free pathway is highly demanded. The recent success of SO 2 fixation by N-heterocyclic carbenes instigated further studies in this regard. Previous reports were confined within the carbene−SO 2 reaction mechanism and the stability of oxathiirane S-oxide derivatives. The complete conversion of captured SO 2 to precious chemicals was not studied. The present inquisition has accomplished the scarcity of the earlier studies. It is observed that in the presence of an excess amount of carbene, the registered SO 2 is converted to the ketone derivative and thiocarbonyl S-oxide derivative. An electronic level investigation of these reactions is carried out. From the change of the molecular orbitals along the reaction path, it is concluded that the reaction between the oxathiirane S-oxide derivative and carbene follows a frog's hunting mechanism.

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Section: Introductionmentioning

confidence: 99%

Schematic Design of Metal-Free NHC-Mediated Sequestering and Complete Conversion of SO₂ to Thiocarbonyl S-Oxide Derivatives at Room Temperature

2022

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“…Using bis(guanidinato)silylenes the reaction with SO 2 in hexane resulted in the formation of a six-coordinate sulfitosilicon( iv ) species whereas in liquid SO 2 a dithionitosilicon( iv ) complex was obtained, in which S–S-coupling was achieved (Scheme 1, iv). 46 The potential of ionic liquids in SO 2 capture has been thoroughly investigated. For example, using tetraethylammonium tetrazolate and ethylene glycol at a molar ratio of 1 : 2, effective SO 2 capture at low SO 2 concentrations was documented (Scheme 1, v).…”

Section: Introductionmentioning

confidence: 99%

Deoxygenation of chalcogen oxides EO₂ (E = S, Se) with phospha-Wittig reagents

et al. 2022

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Iron(II), Cobalt(II), Nickel(II), and Zinc(II) Silylene Complexes: Reaction of the Silylene [iPrNC(NiPr₂)NiPr]₂Si with FeBr₂, CoBr₂, NiBr₂⋅MeOCH₂CH₂OMe, ZnCl₂, and ZnBr₂

Baus

Mück

Schneider

et al. 2016

Chemistry A European J

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Reaction of the donor-stabilized silylene [iPrNC(NiPr )NiPr] Si (1) with FeBr , CoBr , NiBr ⋅MeOCH CH OMe, ZnCl , and ZnBr afforded the respective transition-metal silylene complexes 4-8, the formation of which can be described in terms of a Lewis acid/base reaction (4, 5, 7, 8) or a nucleophilic substitution reaction (6). However, the reactivity profile of silylene 1 is not only based on its strong Lewis base character; the different coordination modes of the two guanidinato ligands (4-6 vs. 7 and 8) add an additional reactivity facet. The paramagnetic compounds 4 and 5 and the diamagnetic compounds 6⋅THF, 7, and 8⋅0.5 Et O were structurally characterized by single-crystal X-ray diffraction. In addition, compound 6⋅THF was studied by N and Si solid-state NMR spectroscopy, and 7 and 8 were characterized by NMR spectroscopic studies in the solid state ( N, Si) and in solution ( H, C, Si). Compounds 4-8 represent very rare examples of Fe , Co , Ni , and Zn silylene complexes. Four-coordinate silicon(II) compounds with an SiN M skeleton (M=Fe, Co, Ni) and M in the formal oxidation state +2 (4-6) have not yet been reported, and five-coordinate silicon(II) compounds with an SiN Zn skeleton (7, 8) are also unprecedented.

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SO₂ Activation by the Bis(guanidinato)silylene [iPrNC(NiPr₂)NiPr]₂Si: Formation of Neutral Six‐Coordinate Silicon(IV) Complexes with a Chelating Sulfito or Dithionito Ligand

Cited by 8 publications

References 35 publications

Schematic Design of Metal-Free NHC-Mediated Sequestering and Complete Conversion of SO₂ to Thiocarbonyl S-Oxide Derivatives at Room Temperature

Schematic Design of Metal-Free NHC-Mediated Sequestering and Complete Conversion of SO₂ to Thiocarbonyl S-Oxide Derivatives at Room Temperature

Deoxygenation of chalcogen oxides EO₂ (E = S, Se) with phospha-Wittig reagents

Iron(II), Cobalt(II), Nickel(II), and Zinc(II) Silylene Complexes: Reaction of the Silylene [iPrNC(NiPr₂)NiPr]₂Si with FeBr₂, CoBr₂, NiBr₂⋅MeOCH₂CH₂OMe, ZnCl₂, and ZnBr₂

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SO2 Activation by the Bis(guanidinato)silylene [iPrNC(NiPr2)NiPr]2Si: Formation of Neutral Six‐Coordinate Silicon(IV) Complexes with a Chelating Sulfito or Dithionito Ligand

Cited by 8 publications

References 35 publications

Schematic Design of Metal-Free NHC-Mediated Sequestering and Complete Conversion of SO2 to Thiocarbonyl S-Oxide Derivatives at Room Temperature

Schematic Design of Metal-Free NHC-Mediated Sequestering and Complete Conversion of SO2 to Thiocarbonyl S-Oxide Derivatives at Room Temperature

Deoxygenation of chalcogen oxides EO2 (E = S, Se) with phospha-Wittig reagents

Iron(II), Cobalt(II), Nickel(II), and Zinc(II) Silylene Complexes: Reaction of the Silylene [iPrNC(NiPr2)NiPr]2Si with FeBr2, CoBr2, NiBr2⋅MeOCH2CH2OMe, ZnCl2, and ZnBr2

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SO₂ Activation by the Bis(guanidinato)silylene [iPrNC(NiPr₂)NiPr]₂Si: Formation of Neutral Six‐Coordinate Silicon(IV) Complexes with a Chelating Sulfito or Dithionito Ligand

Schematic Design of Metal-Free NHC-Mediated Sequestering and Complete Conversion of SO₂ to Thiocarbonyl S-Oxide Derivatives at Room Temperature

Schematic Design of Metal-Free NHC-Mediated Sequestering and Complete Conversion of SO₂ to Thiocarbonyl S-Oxide Derivatives at Room Temperature

Deoxygenation of chalcogen oxides EO₂ (E = S, Se) with phospha-Wittig reagents

Iron(II), Cobalt(II), Nickel(II), and Zinc(II) Silylene Complexes: Reaction of the Silylene [iPrNC(NiPr₂)NiPr]₂Si with FeBr₂, CoBr₂, NiBr₂⋅MeOCH₂CH₂OMe, ZnCl₂, and ZnBr₂