N Functionalization via Molybdenum-Nitride Complex: Stepwise BH Bond Additions.

Reactivity of (triphosphine)Mo-nitrido complex generated by N splitting, toward boranes is reported. The simple adduct Mo≡N→BH is observed with BH.SMe while 1,2 addition is evidenced with 9-BBN leading to H-Mo=NBR.

Assessing Combinations of B(C F ) and N -Derived Molybdenum Nitrido Complexes for Heterolytic Bond Activation.

Two different dinitrogen-derived molybdenum nitrido complexes varying by their geometry, ligand spheres and oxidations states were shown to engage their N ligand in dative bonding with the strong Lewis acid B(C F ) . The stable adducts were assessed for frustrated Lewis pair-type heterolytic E-H bond splitting of hydrosilanes (E=Si) and HB(C F ) . Whereas Si-H bond activation was achieved, HB(C F ) was shown to substitute B(C F ) in a quantitative or equilibrated fashion, depending on the nature of the nitrido complex.

Ammonia Synthesis at Room Temperature and Atmospheric Pressure from N : A Boron-Radical Approach.

Ammonia, NH , is an essential molecule, being part of fertilizers. It is currently synthesized via the Haber-Bosch process, from the very stable dinitrogen molecule, N and dihydrogen, H . This process requires high temperatures and pressures, thereby generating ca 1.

Molecular Electrochemical Reductive Splitting of Dinitrogen with a Molybdenum Complex.

Nitrogen reduction under mild conditions (room T and atmospheric P), using a non-fossil source of hydrogen remains a challenge. Molecular metal complexes, notably Mo based, have recently been shown to be active for such nitrogen fixation. We report electrochemical N splitting with a Mo triphosphino complex [(PPP)MoI ], at room temperature and a moderately negative potential.

Catalytic Reduction of N to Borylamine at a Molybdenum Complex.

Catalytic formation of borylamines from atmospheric N is achieved for the first time using a series of homogenous (triphosphine)Mo complexes. Stepwise functionalization of the (triphosphine)Mo-nitrido complex with chloroborane led to the synthesis of the imido complex. Electrochemical characterization of the (PPP)Mo-nitrido and (PPP)Mo-borylimido complexes showed that the latter is much more easily reduced.

Room-Temperature Functionalization of N to Borylamine at a Molybdenum Complex.

Intermolecular, stepwise functionalization by BH bonds of a (triphosphine)Mo -nitrido complex generated by N splitting is reported. The imido-hydride and di-hydride-amido Mo complexes have been isolated and characterized. Addition of PinBH to the [Mo(H) (N(BPin) )] complex at room temperature results in the liberation of borylamines from the metal center.