||A comparative theoretical study of the hydride transfer mechanisms during LiAlH4 and LiBH4 reductions
Hori, Yuta Ida, Tomonori ,
Computational and Theoretical Chemistry
93 , 2016-01-15 , Elsevier
This work examined the hydride transfer processes during the reduction of formaldehyde by LiAlH4 or LiBH4, including investigations of the geometries, solvent effects and charge transfer processes along the reaction coordinate, using density functional theory (DFT). The energy and geometry results demonstrate that the transition state (TS) structure for the LiAlH4-formaldehyde complex is reactant-like, while the structure generated by LiBH4 has a product-like geometry, consistent with the Hammond postulate. From a charge density analysis, we also found that both complexes undergo the same essential hydride transfer mechanism, which consists of: (1) single electron transfer to the carbonyl carbon, (2) formation of a bridge bond (X-H-C; X=Al or B) and (3) hydrogen transfer driven by electron transfer. Subsequently, in a fourth step, a single electron flows through the X-H-C bond during transfer of the hydrogen, such that hydrogen atom or proton-coupled electron transfer occurs. In both systems, the presence of tetrahydrofuran as a solvent affects the structure and energy values during the reaction, but not the charge transfer characteristics. We propose that the rate-determining steps during hydride transfer when employing LiAlH4 and LiBH4 are one electron transfer to the carbonyl carbon and B-H bond dissociation, respectively. © 2015 Elsevier B.V.