Complexes of Ge(IV)- and Sn(IV)-Fluorides with Cyclic and Acyclic Carbenes: Bis(dialkylamino)-difluoromethylenes as Carbene Sources

Carbene complexes of Ge­(IV)- and Sn­(IV)-fluorides have been synthesized by oxidative addition of 2,2-difluoro-1,3-dimethylimidazolidine and bis­(dimethylamino)­difluoromethane to GeCl₂•dioxane and SnF₂. Chloride analogs of the Ge­(IV) complexes were also isolated. All compounds were characterized in the solid state by single-crystal X-ray diffraction

Phosphorus(V) Complexes with Acyclic Monoaminocarbene Ligands via Oxidative Addition

(Difluoroorganyl)­dimethylamines, RCF₂NMe₂ (R = H, Ph, <i>t</i>Bu), can be used as carbene precursors for phosphorus trifluoride in an oxidative addition reaction. By this method, complexes of sterically nondemanding asymmetric and acyclic carbenes were obtained that are otherwise not accessible

Phosphorus(V) Complexes with Acyclic Monoaminocarbene Ligands via Oxidative Addition

(Difluoroorganyl)­dimethylamines, RCF₂NMe₂ (R = H, Ph, <i>t</i>Bu), can be used as carbene precursors for phosphorus trifluoride in an oxidative addition reaction. By this method, complexes of sterically nondemanding asymmetric and acyclic carbenes were obtained that are otherwise not accessible

Phosphorus(V) Complexes with Acyclic Monoaminocarbene Ligands via Oxidative Addition

(Difluoroorganyl)­dimethylamines, RCF₂NMe₂ (R = H, Ph, <i>t</i>Bu), can be used as carbene precursors for phosphorus trifluoride in an oxidative addition reaction. By this method, complexes of sterically nondemanding asymmetric and acyclic carbenes were obtained that are otherwise not accessible

Carbene Complexes of Phosphorus(V) Fluorides by Oxidative Addition of 2,2-Difluorobis(dialkylamines) to Phosphorus(III) Halides

Carbene-stabilized complexes of substituted and unsubstituted phosphorus­(V) fluorides were obtained by oxidative addition of 2,2-difluorobis­(dialkylamines) to phosphorus­(III) halides. Octahedral and hydrolytically stable complexes were obtained in quantitative yields. All compounds were characterized in the solid state by single-crystal X-ray diffraction

Carbene Complexes of Phosphorus(V) Fluorides by Oxidative Addition of 2,2-Difluorobis(dialkylamines) to Phosphorus(III) Halides

Carbene-stabilized complexes of substituted and unsubstituted phosphorus­(V) fluorides were obtained by oxidative addition of 2,2-difluorobis­(dialkylamines) to phosphorus­(III) halides. Octahedral and hydrolytically stable complexes were obtained in quantitative yields. All compounds were characterized in the solid state by single-crystal X-ray diffraction

SF₅‑Enolates in Ti(IV)-Mediated Aldol Reactions

The F···Ti bonding in the transition structures determines high <i>trans</i>- and <i>syn</i>-diastereoselectivities for aldol reactions of SF₅-acetates with aldehydes in the presence of TiCl₄ in the non-nucleophilic solvent CH₂Cl₂. Such bonding is canceled in nucleophilic solvents where opposite <i>cis</i>-stereochemistry is observed. The potential of thus obtained stereoisomeric SF₅-aryl acrylates as dipolarophiles in the preparation of SF₅-containing heterocycles is demonstrated

SF₅‑Enolates in Ti(IV)-Mediated Aldol Reactions

The F···Ti bonding in the transition structures determines high <i>trans</i>- and <i>syn</i>-diastereoselectivities for aldol reactions of SF₅-acetates with aldehydes in the presence of TiCl₄ in the non-nucleophilic solvent CH₂Cl₂. Such bonding is canceled in nucleophilic solvents where opposite <i>cis</i>-stereochemistry is observed. The potential of thus obtained stereoisomeric SF₅-aryl acrylates as dipolarophiles in the preparation of SF₅-containing heterocycles is demonstrated

SF₅‑Enolates in Ti(IV)-Mediated Aldol Reactions

The F···Ti bonding in the transition structures determines high <i>trans</i>- and <i>syn</i>-diastereoselectivities for aldol reactions of SF₅-acetates with aldehydes in the presence of TiCl₄ in the non-nucleophilic solvent CH₂Cl₂. Such bonding is canceled in nucleophilic solvents where opposite <i>cis</i>-stereochemistry is observed. The potential of thus obtained stereoisomeric SF₅-aryl acrylates as dipolarophiles in the preparation of SF₅-containing heterocycles is demonstrated

SF₅‑Enolates in Ti(IV)-Mediated Aldol Reactions

The F···Ti bonding in the transition structures determines high <i>trans</i>- and <i>syn</i>-diastereoselectivities for aldol reactions of SF₅-acetates with aldehydes in the presence of TiCl₄ in the non-nucleophilic solvent CH₂Cl₂. Such bonding is canceled in nucleophilic solvents where opposite <i>cis</i>-stereochemistry is observed. The potential of thus obtained stereoisomeric SF₅-aryl acrylates as dipolarophiles in the preparation of SF₅-containing heterocycles is demonstrated