Structural and Thermochemical Studies of Pyrrolidine Borane and Piperidine Borane by Gas Electron Diffraction and Quantum Chemical Calculations

TY - JOUR

T1 - Structural and Thermochemical Studies of Pyrrolidine Borane and Piperidine Borane by Gas Electron Diffraction and Quantum Chemical Calculations

AU - Ja’o, Aliyu M.

AU - Wann, Derek A.

AU - Rankine, Conor D.

AU - Nunes, João P.F.

AU - Guillemin, Jean Claude

AU - Masters, Sarah L.

N1 - © 2020 Springer Science+Business Media, LLC, part of Springer Nature. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

PY - 2021/2/1

Y1 - 2021/2/1

N2 - The gaseous structures, thermochemical properties and dehydrogenation reaction energy profiles of the borane complexes of pyrrolidine and piperidine have been investigated using gas electron diffraction (GED) and state-of-the-art computational methods. These complexes are of interest because of their potential as hydrogen storage materials for future onboard transport applications. A comparative structural and thermochemical analysis revealed structures with a slight difference in the essential B–N bond length, with the piperidine borane having a longer bond even though it has a stronger B–N bond according to predicted bond dissociation energies, a trend common with amine boranes. To identify the most favourable dehydrogenation pathway, BH3-catalysed and BH3-uncatalysed dehydrogenation channels have been explored, where the former has been shown to be the favourable process for both complexes. The energy requirements for the hydrogen release reactions are expected to be minimal as evidenced from the calculated dehydrogenation reaction energies, implying their suitability for onboard chemical hydrogen storage.

AB - The gaseous structures, thermochemical properties and dehydrogenation reaction energy profiles of the borane complexes of pyrrolidine and piperidine have been investigated using gas electron diffraction (GED) and state-of-the-art computational methods. These complexes are of interest because of their potential as hydrogen storage materials for future onboard transport applications. A comparative structural and thermochemical analysis revealed structures with a slight difference in the essential B–N bond length, with the piperidine borane having a longer bond even though it has a stronger B–N bond according to predicted bond dissociation energies, a trend common with amine boranes. To identify the most favourable dehydrogenation pathway, BH3-catalysed and BH3-uncatalysed dehydrogenation channels have been explored, where the former has been shown to be the favourable process for both complexes. The energy requirements for the hydrogen release reactions are expected to be minimal as evidenced from the calculated dehydrogenation reaction energies, implying their suitability for onboard chemical hydrogen storage.

KW - Amine Boranes

KW - Dehydrogenation

KW - Gas Electron Diffraction

KW - Hydrogen Storage

UR - http://www.scopus.com/inward/record.url?scp=85092239203&partnerID=8YFLogxK

U2 - 10.1007/s11224-020-01647-0

DO - 10.1007/s11224-020-01647-0

M3 - Article

AN - SCOPUS:85092239203

SN - 1040-0400

VL - 32

SP - 205

EP - 213

JO - Structural Chemistry

JF - Structural Chemistry

ER -