Post-Synthesis Amine Borane Functionalization of a Metal-Organic Framework and Its Unusual Chemical Hydrogen Release Phenomenon

Samir Barman; Arndt Remhof; Ralph Koitz; Marcella Iannuzzi; Olivier Blacque; Yigang Yan; Thomas Fox; Jürg Hutter; Andreas Züttel; Heinz Berke

doi:10.1002/chem.201702013

Post-Synthesis Amine Borane Functionalization of a Metal-Organic Framework and Its Unusual Chemical Hydrogen Release Phenomenon

Samir Barman, Arndt Remhof, Ralph Koitz, Marcella Iannuzzi, Olivier Blacque, Yigang Yan, Thomas Fox, Jürg Hutter, Andreas Züttel, Heinz Berke^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

A novel strategy for post-synthesis amine borane functionalization of MOFs under gas-solid phase transformation, utilizing gaseous diborane, is reported. The covalently confined amine borane derivative decorated on the framework backbone is stable when preserved at low temperature, but spontaneously liberates soft chemical hydrogen at room temperature, leading to the development of an unusual borenium type species (-NH=BH₂⁺) ion-paired with a hydroborate anion. Furthermore, the unsaturated amino borane (-NH=BH₂) and the μ-iminodiborane (-μ-NHB₂H₅) were detected as final products. A combination of DFT based molecular dynamics simulations and solid state NMR spectroscopy, utilizing isotopically enriched materials, were undertaken to unequivocally elucidate the mechanistic pathways for H₂ liberation.

Original language	English
Pages (from-to)	8823-8828
Number of pages	6
Journal	Chemistry - A European Journal
Volume	23
Issue number	37
DOIs	https://doi.org/10.1002/chem.201702013
State	Published - 3 Jul 2017
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

amine boranes
density functional theory
metal-organic frameworks
molecular dynamics calculations
solid state NMR spectroscopy

ASJC Scopus subject areas

Catalysis
General Chemistry
Organic Chemistry

Access to Document

10.1002/chem.201702013

Cite this

@article{2fb688a163ba4e879364ba4736c2ccf6,

title = "Post-Synthesis Amine Borane Functionalization of a Metal-Organic Framework and Its Unusual Chemical Hydrogen Release Phenomenon",

abstract = "A novel strategy for post-synthesis amine borane functionalization of MOFs under gas-solid phase transformation, utilizing gaseous diborane, is reported. The covalently confined amine borane derivative decorated on the framework backbone is stable when preserved at low temperature, but spontaneously liberates soft chemical hydrogen at room temperature, leading to the development of an unusual borenium type species (-NH=BH2+) ion-paired with a hydroborate anion. Furthermore, the unsaturated amino borane (-NH=BH2) and the μ-iminodiborane (-μ-NHB2H5) were detected as final products. A combination of DFT based molecular dynamics simulations and solid state NMR spectroscopy, utilizing isotopically enriched materials, were undertaken to unequivocally elucidate the mechanistic pathways for H2 liberation.",

keywords = "amine boranes, density functional theory, metal-organic frameworks, molecular dynamics calculations, solid state NMR spectroscopy",

author = "Samir Barman and Arndt Remhof and Ralph Koitz and Marcella Iannuzzi and Olivier Blacque and Yigang Yan and Thomas Fox and J{\"u}rg Hutter and Andreas Z{\"u}ttel and Heinz Berke",

note = "Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2017",

month = jul,

day = "3",

doi = "10.1002/chem.201702013",

language = "English",

volume = "23",

pages = "8823--8828",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley and Sons Inc.",

number = "37",

}

TY - JOUR

T1 - Post-Synthesis Amine Borane Functionalization of a Metal-Organic Framework and Its Unusual Chemical Hydrogen Release Phenomenon

AU - Barman, Samir

AU - Remhof, Arndt

AU - Koitz, Ralph

AU - Iannuzzi, Marcella

AU - Blacque, Olivier

AU - Yan, Yigang

AU - Fox, Thomas

AU - Hutter, Jürg

AU - Züttel, Andreas

AU - Berke, Heinz

PY - 2017/7/3

Y1 - 2017/7/3

N2 - A novel strategy for post-synthesis amine borane functionalization of MOFs under gas-solid phase transformation, utilizing gaseous diborane, is reported. The covalently confined amine borane derivative decorated on the framework backbone is stable when preserved at low temperature, but spontaneously liberates soft chemical hydrogen at room temperature, leading to the development of an unusual borenium type species (-NH=BH2+) ion-paired with a hydroborate anion. Furthermore, the unsaturated amino borane (-NH=BH2) and the μ-iminodiborane (-μ-NHB2H5) were detected as final products. A combination of DFT based molecular dynamics simulations and solid state NMR spectroscopy, utilizing isotopically enriched materials, were undertaken to unequivocally elucidate the mechanistic pathways for H2 liberation.

AB - A novel strategy for post-synthesis amine borane functionalization of MOFs under gas-solid phase transformation, utilizing gaseous diborane, is reported. The covalently confined amine borane derivative decorated on the framework backbone is stable when preserved at low temperature, but spontaneously liberates soft chemical hydrogen at room temperature, leading to the development of an unusual borenium type species (-NH=BH2+) ion-paired with a hydroborate anion. Furthermore, the unsaturated amino borane (-NH=BH2) and the μ-iminodiborane (-μ-NHB2H5) were detected as final products. A combination of DFT based molecular dynamics simulations and solid state NMR spectroscopy, utilizing isotopically enriched materials, were undertaken to unequivocally elucidate the mechanistic pathways for H2 liberation.

KW - amine boranes

KW - density functional theory

KW - metal-organic frameworks

KW - molecular dynamics calculations

KW - solid state NMR spectroscopy

UR - https://www.scopus.com/pages/publications/85020406389

U2 - 10.1002/chem.201702013

DO - 10.1002/chem.201702013

M3 - Article

C2 - 28493380

AN - SCOPUS:85020406389

SN - 0947-6539

VL - 23

SP - 8823

EP - 8828

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 37

ER -

Post-Synthesis Amine Borane Functionalization of a Metal-Organic Framework and Its Unusual Chemical Hydrogen Release Phenomenon

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

Fingerprint

Cite this