PNNL

Abstract

We report a combined computational and experimental study of the activation of hydrogen using for 2,6-lutidine/trichloroborane (Lut/BCl3) Lewis pairs. We show that Lut·BCl3 activates molecular H2 at ~10 bar, 100 °C in toluene, bromobenzene, dichloromethane and in lutidine as solvent. The resulting product is an unexpected neutral hydride, LutBHCl2, which we attribute to ligand redistribution between BCl3 and [LutH+][HBCl3–] ion pair. The mechanism for activation was modeled with density functional theory and accurate G3(MP2)B3 theory. This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences, and Geosciences, and was performed in part using the Molecular Science Computing Facilities in the William R. Wiley Environmental Molecular Sciences Laboratory, a DOE national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for DOE.