Sébastien Bontemps

Ruthenium-Catalyzed Reduction of Carbon Dioxide to Formaldehyde

Functionalization of CO2 is a challenging goal and precedents exist for the generation of HCOOH, CO, CH3OH, and CH4 in mild conditions. In this series, CH2O, a very reactive molecule, remains an elementary C1 building block to be observed. Herein we report the direct observation of free formaldehyde from the borane reduction of CO2 catalyzed by a polyhydride ruthenium complex. Guided by mechanistic studies, we disclose the selective trapping of formaldehyde by in situ condensation with a primary amine into the corresponding imine in very mild conditions. Subsequent hydrolysis into amine and a formalin solution demonstrates for the first time that CO2 can be used as a C1 feedstock to produce formaldehyde.

Iron-Catalyzed C–H Borylation of Arenes

Well-defined iron bis(diphosphine) complexes are active catalysts for the dehydrogenative C-H borylation of aromatic and heteroaromatic derivatives with pinacolborane. The corresponding borylated compounds were isolated in moderate to good yields (25-73%) with a 5 mol% catalyst loading under UV irradiation (350 nm) at room temperature. Stoichiometric reactivity studies and isolation of an original trans-hydrido(boryl)iron complex, Fe(H)(Bpin)(dmpe)2, allowed us to propose a mechanism showing the role of some key catalytic species.

Iron-Catalyzed Reduction of CO2 into Methylene: Formation of C-N, C-O, and C-C Bonds.

We report herein the use of the (dihydrido)iron catalyst, Fe(H)2(dmpe)2, for the selective reduction of CO2 into either bis(boryl)acetal or methoxyborane depending on the hydroborane used as a reductant. In a one-pot two-step procedure, the in situ generated bis(boryl)acetal was shown to be a reactive and versatile source of methylene to create new C-N but also C-O and C-C bonds.

Two-Coordinate Iron(I) Complex [Fe{N(SiMe3)2}2]−: Synthesis, Properties, and Redox Activity†

First-row two-coordinate complexes are attracting much interest. Herein, we report the high-yield isolation of the linear two-coordinate iron(I) complex salt [K(L)][Fe{N(SiMe3 )2 }2 ] (L=18-crown-6 or crypt-222) through the reduction of either [Fe{N(SiMe3 )2 }2 ] or its three-coordinate phosphine adduct [Fe{N(SiMe3 )2 }2 (PCy3 )]. Detailed characterization is gained through X-ray diffraction, variable-temperature NMR spectroscopy, and magnetic susceptibility studies. One- and two-electron oxidation through reaction with I2 is further found to afford the corresponding iodo iron(II) and diiodo iron(III) complexes.

A 1,1′-ferrocenyl phosphine-borane: synthesis, structure and evaluation in Rh-catalyzed hydroformylation

The new ambiphilic ligand Ph2P–(1,1′-ferrocenyl)–BMes2, prepared by sequential lithiation/electrophilic trapping of 1,1′-dibromoferrocene, adopts a monomeric structure free of dative P → B and Fe → B interactions. This flexible phosphine-borane and the related o-phenylene bridged system have been evaluated in Rh-catalyzed hydroformylation.

Homoleptic Two-Coordinate Silylamido Complexes of Chromium(I), Manganese(I), and Cobalt(I).

Anionic two-coordinate complexes of first-row transition-metal(I) centres are rare molecules that are expected to reveal new magnetic properties and reactivity. Recently, we demonstrated that a N(SiMe3)2(-) ligand set, which is unable to prevent dimerisation or extraneous ligand coordination at the +2 oxidation state of iron, was nonetheless able to stabilise anionic two-coordinate Fe(I) complexes even in the presence of a Lewis base. We now report analogous Cr(I) and Co(I) complexes with exclusively this amido ligand and the isolation of a [Mn(I){N(SiMe3)2}2]2(2-) dimer that features a Mn-Mn bond. Additionally, by increasing the steric hindrance of the ligand set, the two-coordinate complex [Mn(I){N(Dipp)(SiMe3)}2](-) was isolated (Dipp=2,6-iPr2-C6H3). Characterisation of these compounds by using X-ray crystallography, NMR spectroscopy, and magnetic susceptibility measurements is provided along with ligand-field analysis based on CASSCF/NEVPT2 ab initio calculations.