CO 2 Reduction by Lanthanum Borohydride Complexes and Hydroboration Reactivity

Le résumé fourni par la source

Although lanthanide borohydride precursors are useful building blocks to access molecular lanthanide complexes, the nucleophilic reactivity of the attached [BH 4 ] − unit has not been thoroughly investigated. We herein report the reaction of [La(Cp ttt ) 2 (BH 4 )] ( 1, Cp ttt = 1,2,4-tris( tert -butyl)cyclopentadienyl) toward CO 2, leading to the formation of a formate complex, which exists as an equilibrium mixture between the dimeric and monomeric forms in aromatic solvents. 1 H DOSY NMR experiments allowed a convenient analysis of the reaction mixture and provided an estimation of the hydrodynamic radii for both species. Hydroborane reagents (BH 3, HBPin, H(9-BBN)) further react with the formate complex, leading to the formation of borylated methanol and the corresponding lanthanide boroxide complexes. Preliminary investigations were performed to investigate the viability of 1 as a precatalyst in the hydroboration of CO 2 . This work highlights the potential application of readily available rare-earth borohydride complexes in the transformation and valorization of CO 2 .

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