Eddy Maerten

A persistent C ‐phosphonio boratavinyl anion 1 has been successfully synthesized. This boron‐containing vinyl‐lithium 1 , featuring a vinyl carbon with a negative charge (−1.59), considerably higher than that of carbon analogue 7 (−0.76), exhibits strongly nucleophilic and basic properties, as demonstrated by the results of rapid reactions with H ₂ (10 bar, 15 min or 1 bar, 2 h at RT) and C ₆ F ₆ (1 equiv., 15 min at −80°C). The reactions of boratavinyl anion 1 with electrophiles offer a convenient route for the introduction of a borata‐alkene‐based bulky and σ,π‐double‐donating substituent, enabling to efficiently stabilize reactive intermediates such as halogenogermylenes. Furthermore, the reaction with CO ₂ takes place at the borata‐alkene moiety, rather than at the P‐ylide function, resulting in the double insertion of CO ₂ into the B─C bond to afford a unique cyclic P‐ylide 13 .

A persistent C ‐phosphonio boratavinyl anion 1 has been successfully synthesized. This boron‐containing vinyl‐lithium 1 , featuring a vinyl carbon with a negative charge (−1.59), considerably higher than that of carbon analogue 7 (−0.76), exhibits strongly nucleophilic and basic properties, as demonstrated by the results of rapid reactions with H ₂ (10 bar, 15 min or 1 bar, 2 h at RT) and C ₆ F ₆ (1 equiv., 15 min at −80°C). The reactions of boratavinyl anion 1 with electrophiles offer a convenient route for the introduction of a borata‐alkene‐based bulky and σ,π‐double‐donating substituent, enabling to efficiently stabilize reactive intermediates such as halogenogermylenes. Furthermore, the reaction with CO ₂ takes place at the borata‐alkene moiety, rather than at the P‐ylide function, resulting in the double insertion of CO ₂ into the B─C bond to afford a unique cyclic P‐ylide 13 .

The development of efficient catalysts for CO ₂ transformation into value-added products is crucial for sustainable chemistry.

In this work, a new asymmetric amidine–imine ligand, using 1,8-diaminonaphthalene as a rigid platform, was synthesized and characterized, and its ability to form complexes with aluminum(III) was investigated. Several aluminum complexes were synthesized and characterized in solution and in the solid state. The synthesis of a dihalogenated aluminum(III) complex (AlI₂L) using a reducing agent revealed an atypical pathway, which was investigated using Density Functional Theory (DFT). The dimethylated aluminum complex AlMe₂L and the dihalogenated aluminum complex AlI₂L were evaluated as catalysts for the transformation of CO₂ and epoxides into cyclic carbonates in the presence of Bu₄NI as a co-catalyst or in a single-component system, respectively. AlMe₂L/Bu₄NI appeared to be the most efficient system under 1 bar of CO₂ at 90 °C.

On-surface chemistry aims to overcome the limitations of conventional in-solution synthesis by taking advantage of the confinement in two dimensions to master highly ordered covalent structures with tailored properties. So far, most of the reported work is conducted on metal substrates and relies on unconventional mechanisms, thereby precluding a direct transposition of well-established organic reactions from solutions to surfaces. In addition, the intrinsic properties and reactivity of metal substrates often limit the activation methods available to trigger on-surface reactions, and photoinduced processes are especially difficult to handle due to quenching of the adsorbed precursor molecules. Herein, the photoinduced deoxygenation of dibenzothiophene S-oxide (DBTO) derivatives is transposed from solutions to insulating alkali halide surfaces in ultra-high vacuum. By combining in-solution and on-surface investigations by means of scanning tunneling microscopy, non-contact atomic force microscopy, as well as bias spectroscopy measurements, we provide evidence of the successful on-surface deoxygenation of individual DBTO derivatives under UV irradiation. The photoinduced deoxygenation is conducted at low temperature (<25 K) on a NaCl thin film formed on a Au(111) substrate to yield the reduced dibenzothiophene (DBT) product with excellent chemoselectivity. This work thus opens the way to in-situ photocontrolled charge state manipulation in purely organic compounds.

A series of organometallic complexes is reported to demonstrate the versatility in coordination mode of phosphine/sulfoxide carbone. Early and late transition metals can be chelated, in a mono- or bidentate fashion depending on the metal center.

On-surface chemistry aims to overcome the limitations of conventional in-solution synthesis by taking advantage of the confinement in two dimensions to master highly ordered covalent structures with tailored properties. So far, most of the reported work was conducted on metal substrates and relied on unconventional mechanisms, thereby precluding a direct transposition of well-established organic reactions from solutions to surfaces. In addition, the intrinsic properties and reactivity of metal substrates often limit the activation methods available to trigger on-surface reactions, and photoinduced processes are especially difficult to handle due to quenching of the adsorbed precursor molecules. Herein, the photoinduced deoxygenation of dibenzothiophene S-oxide (DBTO) derivatives was transposed from solutions to insulating alkali halide surfaces in ultra-high vacuum. By combining in-solution and on-surface investigations by means of scanning tunneling microscopy, non-contact atomic force microscopy, as well as Bias spectroscopy measurements, we provide evidence of the successful on-surface deoxygenation of individual DBTO derivatives under UV irradiation. The photoinduced deoxygenation is conducted at low temperature (< 25 K) on a NaCl thin film formed on a Au(111) substrate to yield the reduced dibenzothiophene (DBT) product with excellent chemoselectivity. This work thus opens the way to in-situ photocontrolled charge state manipulation in purely organic compounds.

Tetrahydro-4H-thiopyran-4-one 1-oxide 1 and sulfinyl-di-tert-butylpropionate 2 were reported as sources of bis-sulfenate anion and applied in a double pallado-catalyzed cross-coupling reaction for the synthesis of symmetrical biarylsulfoxides, tolerating a large array of electronic properties and bulkiness. The photophysical properties of a biarylsulfoxide have been explored, demonstrating an unreported TADF phenomenon on sulfoxide-containing scaffolds.

Pentafluorophenyl copper(I)–biarylsulfoxide complexes, existing as [Cu(C₆F₅)]₄L₂, both in solution and in the solid state, were prepared and thoroughly characterized. Subsequently, the photochemistry of the complexes was explored, showing inherent photoreactivity of the biarylsulfoxide moiety within the coordination sphere of the copper. Photoinduced cross-coupling reactions between the anthryl moiety of bis-anthracenylsulfoxide and pentafluorobenzene, and synthesis of Cu₂O (cuprite), were demonstrated.

Tetrahydro-4H-thiopyran-4-one 1-oxide 1 and sulfinyl-di-tert-butylpropionate 2 were reported as sources of bis-sulfenate anion and applied in a double pallado-catalyzed cross-coupling reaction for the synthesis of symmetrical biarylsulfoxides, tolerating a large array of electronic properties and bulkiness. The photophysical properties of a biarylsulfoxide have been explored, demonstrating an unreported TADF phenomenon on sulfoxide-containing scaffolds.