BIFUN

Associating two research groups with complementary expertise, the cooperative project BIFUN aims at developing bifunctional activator-free Ni(II)-NHC (NHC = N-heterocyclic carbene) catalysts for the hydroboration and hydrosilylation of alkenes by cooperative E–H (E = B, Si) bond activation. For that purpose, BIFUN proposes an approach that relies on a three-pronged strategy: (i) predictive and analytical DFT to evaluate the thermodynamics of the cooperative E–H bond activation for a small set of privileged structures of potential Ni(II)-NHC precatalysts comprising a labile or remote nickel-unbonded nucleophilic site for borane coordination and a Lewis acidic nickel centre for hydride capture, whose preparation feasibility will be established by model synthesis tries and reactivity explored by preliminary catalytic runs at the onset of the project, (ii) in-depth experimental studies with the most promising catalytic systems identified by the predictive calculations that include, in addition to classical catalytic and intermediates’ trapping studies, isothermal calorimetric titrations and non-intrusive kinetic measurements of elementary steps, (iii) analytical DFT to rationalize the inputs of the experimental studies. In addition to deliver effective activator-free bifunctional Ni-NHC catalysts for the hydroboration and hydrosilylation of alkenes, BIFUN expects, through an interdisciplinary methodology, to provide an understanding of the parameters that govern the reactivity and selectivity for the studied systems, and beyond to define the future challenges to overcome for designing the most possible efficient and sustainable catalytic systems for these two important transformations.