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Title: Mechanism of Solid-State Thermolysis of Ammonia Boraine: 15N NMR Study Using Fast Magic-Angle Spinning and Dynamic Nuclear Polarization

Abstract

The solid-state thermolysis of ammonia borane (NH3BH3, AB) was explored using state-of-the-art 15N solid-state NMR spectroscopy, including 2D indirectly detected 1H{15N} heteronuclear correlation and dynamic nuclear polarization (DNP)-enhanced 15N{1H} cross-polarization experiments as well as 11B NMR. The complementary use of 15N and 11B NMR experiments, supported by density functional theory calculations of the chemical shift tensors, provided insights into the dehydrogenation mechanism of AB—insights that have not been available by 11B NMR alone. Specifically, highly branched polyaminoborane derivatives were shown to form from AB via oligomerization in the “head-to-tail” manner, which then transform directly into hexagonal boron nitride analog through the dehydrocyclization reaction, bypassing the formation of polyiminoborane.

Authors:
 [1];  [1];  [2];  [1];  [1]
  1. Ames Laboratory
  2. Bruker BioSpin Corporation
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1166713
Report Number(s):
IS-J 8452
Journal ID: ISSN 1932-7447
DOE Contract Number:  
DE-AC02-07CH11358
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 118; Journal Issue: 34; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Catalysis, Reaction Kinetics, and Inorganic Reaction Mechanisms

Citation Formats

Kobayashi, Takeshi, Gupta, Shalabh, Caporini, Marc A, Pecharsky, Vitalij K, and Pruski, Marek. Mechanism of Solid-State Thermolysis of Ammonia Boraine: 15N NMR Study Using Fast Magic-Angle Spinning and Dynamic Nuclear Polarization. United States: N. p., 2014. Web. doi:10.1021/jp504328x.
Kobayashi, Takeshi, Gupta, Shalabh, Caporini, Marc A, Pecharsky, Vitalij K, & Pruski, Marek. Mechanism of Solid-State Thermolysis of Ammonia Boraine: 15N NMR Study Using Fast Magic-Angle Spinning and Dynamic Nuclear Polarization. United States. https://doi.org/10.1021/jp504328x
Kobayashi, Takeshi, Gupta, Shalabh, Caporini, Marc A, Pecharsky, Vitalij K, and Pruski, Marek. 2014. "Mechanism of Solid-State Thermolysis of Ammonia Boraine: 15N NMR Study Using Fast Magic-Angle Spinning and Dynamic Nuclear Polarization". United States. https://doi.org/10.1021/jp504328x.
@article{osti_1166713,
title = {Mechanism of Solid-State Thermolysis of Ammonia Boraine: 15N NMR Study Using Fast Magic-Angle Spinning and Dynamic Nuclear Polarization},
author = {Kobayashi, Takeshi and Gupta, Shalabh and Caporini, Marc A and Pecharsky, Vitalij K and Pruski, Marek},
abstractNote = {The solid-state thermolysis of ammonia borane (NH3BH3, AB) was explored using state-of-the-art 15N solid-state NMR spectroscopy, including 2D indirectly detected 1H{15N} heteronuclear correlation and dynamic nuclear polarization (DNP)-enhanced 15N{1H} cross-polarization experiments as well as 11B NMR. The complementary use of 15N and 11B NMR experiments, supported by density functional theory calculations of the chemical shift tensors, provided insights into the dehydrogenation mechanism of AB—insights that have not been available by 11B NMR alone. Specifically, highly branched polyaminoborane derivatives were shown to form from AB via oligomerization in the “head-to-tail” manner, which then transform directly into hexagonal boron nitride analog through the dehydrocyclization reaction, bypassing the formation of polyiminoborane.},
doi = {10.1021/jp504328x},
url = {https://www.osti.gov/biblio/1166713}, journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 34,
volume = 118,
place = {United States},
year = {Thu Aug 28 00:00:00 EDT 2014},
month = {Thu Aug 28 00:00:00 EDT 2014}
}