Heterolysis of H2 Across a Classical Lewis Pair, 2,6-Lutidine∙BCl3: Synthesis, Characterization, and Mechanism

Ginovska, Bojana; Autrey, Tom; Parab, Kshitij; Bowden, Mark E.; Potter, Robert G.; Camaioni, Donald M.

doi:10.1002/chem.201501899

Heterolysis of H₂ Across a Classical Lewis Pair, 2,6-Lutidine∙BCl3: Synthesis, Characterization, and Mechanism

Journal Article · Thu Sep 10 04:00:00 EDT 2015 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201501899· OSTI ID:1734875

Ginovska, Bojana ^[1]; ^[1]; Parab, Kshitij ^[1]; Bowden, Mark E. ^[1]; Potter, Robert G. ^[1]; ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

In this study, we report that 2,6-lutidine∙trichloroborane (Lut∙BCl₃) reacts with H₂ in toluene, bromobenzene, dichloromethane, and Lut solvents producing the neutral hydride, Lut∙BHCl₂. The mechanism was modeled with density functional theory, and energies of stationary states were calculated at the G3(MP2)B3 level of theory. Lut∙BCl₃ was calculated to react with H₂ and form the ion pair, [LutH⁺][HBCl₃^–], with a barrier of ΔH^≠=24.7 kcal mol^–1 (ΔG^≠=29.8 kcal mol^–1). Metathesis with a second molecule of Lut∙BCl₃ produced Lut∙BHCl₂ and [LutH⁺][BCl₄^–]. The overall reaction is exothermic by 6.0 kcal mol^–1 (Δ_rG°=–1.1). Alternate pathways were explored involving the borenium cation (LutBCl₂⁺) and the four-membered boracycle [(CH₂{NC₅H₃Me})BCl₂]. Barriers for addition of H₂ across the Lut/LutBCl₂⁺ pair and the boracycle B—C bond are substantially higher (ΔG^≠=42.1 and 49.4 kcal mol^–1, respectively), such that these pathways are excluded. The barrier for addition of H₂ to the boracycle B—N bond is comparable (ΔH^≠=28.5 and ΔG^≠=32 kcal mol^–1). Conversion of the intermediate 2-(BHCl₂CH₂)-6-Me(C₅H₃NH) to Lut∙BHCl₂ may occur by intermolecular steps involving proton/hydride transfers to Lut/BCl₃. Intramolecular protodeboronation, which could form Lut∙BHCl₂ directly, is prohibited by a high barrier (ΔH^≠=52, ΔG^≠=51 kcal mol^–1).

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1734875

Alternate ID(s):: OSTI ID: 1229948

Report Number(s):: PNNL-SA--109925

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 44 Vol. 21; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited By (2)

Reversible hydrogen activation by a bulky haloborane based FLP system Courtemanche, Marc-André; Rochette, Étienne; Légaré, Marc-André Dalton Transactions, Vol. 45, Issue 14 https://doi.org/10.1039/c5dt03916a	journal	January 2016
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