Real-Time Detection of Intermediates in Rhodium Catalyzed Hydrogenation of Alkynes and Alkenes by Dissolution DNP

Peter Andreas Boeg, Jens Øllgaard Duus, Jan Henrik Ardenkjær-Larsen, Magnus Karlsson, Susanne Mossin*

*Corresponding author for this work

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Abstract

The hydrogenation of alkynes and alkenes using a Shrock-Osborn catalysts was followed in-situ with dissolution dynamic nuclear polarization (dDNP) NMR. Natural abundance and 13C labeled dimethyl acetylenedicarboxylate was hyperpolarized prior to hydrogenation using (1,4-bis{diphenylphosphino}butane)(2,5-norbornadiene) rhodium(I) perchlorate, [Rh(NBD)(DPPB)]ClO4. The increased signal-to-noise ratio of dDNP compared to conventional 13C NMR allowed real-time detection of substrate and products as well as the modeling of the hydrogenation kinetics. The build-up of an intermediate was observed during interruption in hydrogen flow, substantiating the current view of the reaction mechanism. Selective inversion of the carbonyl NMR signal of the substrate was applied to demonstrate unequivocally that the new peak appearing in the spectrum originates from a reaction intermediate. The scope of the dDNP method for following reaction dynamics in real time was further demonstrated by substrate competition experiments.
Original languageEnglish
JournalThe Journal of Physical Chemistry Part C
Volume123
Issue number15
Pages (from-to)9949-9956
Number of pages8
ISSN1932-7447
DOIs
Publication statusPublished - 2019

Cite this

@article{a1561329401c477989991ceec81e81fe,
title = "Real-Time Detection of Intermediates in Rhodium Catalyzed Hydrogenation of Alkynes and Alkenes by Dissolution DNP",
abstract = "The hydrogenation of alkynes and alkenes using a Shrock-Osborn catalysts was followed in-situ with dissolution dynamic nuclear polarization (dDNP) NMR. Natural abundance and 13C labeled dimethyl acetylenedicarboxylate was hyperpolarized prior to hydrogenation using (1,4-bis{diphenylphosphino}butane)(2,5-norbornadiene) rhodium(I) perchlorate, [Rh(NBD)(DPPB)]ClO4. The increased signal-to-noise ratio of dDNP compared to conventional 13C NMR allowed real-time detection of substrate and products as well as the modeling of the hydrogenation kinetics. The build-up of an intermediate was observed during interruption in hydrogen flow, substantiating the current view of the reaction mechanism. Selective inversion of the carbonyl NMR signal of the substrate was applied to demonstrate unequivocally that the new peak appearing in the spectrum originates from a reaction intermediate. The scope of the dDNP method for following reaction dynamics in real time was further demonstrated by substrate competition experiments.",
author = "Boeg, {Peter Andreas} and Duus, {Jens {\O}llgaard} and Ardenkj{\ae}r-Larsen, {Jan Henrik} and Magnus Karlsson and Susanne Mossin",
year = "2019",
doi = "10.1021/acs.jpcc.9b01376",
language = "English",
volume = "123",
pages = "9949--9956",
journal = "The Journal of Physical Chemistry Part C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "15",

}

TY - JOUR

T1 - Real-Time Detection of Intermediates in Rhodium Catalyzed Hydrogenation of Alkynes and Alkenes by Dissolution DNP

AU - Boeg, Peter Andreas

AU - Duus, Jens Øllgaard

AU - Ardenkjær-Larsen, Jan Henrik

AU - Karlsson, Magnus

AU - Mossin, Susanne

PY - 2019

Y1 - 2019

N2 - The hydrogenation of alkynes and alkenes using a Shrock-Osborn catalysts was followed in-situ with dissolution dynamic nuclear polarization (dDNP) NMR. Natural abundance and 13C labeled dimethyl acetylenedicarboxylate was hyperpolarized prior to hydrogenation using (1,4-bis{diphenylphosphino}butane)(2,5-norbornadiene) rhodium(I) perchlorate, [Rh(NBD)(DPPB)]ClO4. The increased signal-to-noise ratio of dDNP compared to conventional 13C NMR allowed real-time detection of substrate and products as well as the modeling of the hydrogenation kinetics. The build-up of an intermediate was observed during interruption in hydrogen flow, substantiating the current view of the reaction mechanism. Selective inversion of the carbonyl NMR signal of the substrate was applied to demonstrate unequivocally that the new peak appearing in the spectrum originates from a reaction intermediate. The scope of the dDNP method for following reaction dynamics in real time was further demonstrated by substrate competition experiments.

AB - The hydrogenation of alkynes and alkenes using a Shrock-Osborn catalysts was followed in-situ with dissolution dynamic nuclear polarization (dDNP) NMR. Natural abundance and 13C labeled dimethyl acetylenedicarboxylate was hyperpolarized prior to hydrogenation using (1,4-bis{diphenylphosphino}butane)(2,5-norbornadiene) rhodium(I) perchlorate, [Rh(NBD)(DPPB)]ClO4. The increased signal-to-noise ratio of dDNP compared to conventional 13C NMR allowed real-time detection of substrate and products as well as the modeling of the hydrogenation kinetics. The build-up of an intermediate was observed during interruption in hydrogen flow, substantiating the current view of the reaction mechanism. Selective inversion of the carbonyl NMR signal of the substrate was applied to demonstrate unequivocally that the new peak appearing in the spectrum originates from a reaction intermediate. The scope of the dDNP method for following reaction dynamics in real time was further demonstrated by substrate competition experiments.

U2 - 10.1021/acs.jpcc.9b01376

DO - 10.1021/acs.jpcc.9b01376

M3 - Journal article

VL - 123

SP - 9949

EP - 9956

JO - The Journal of Physical Chemistry Part C

JF - The Journal of Physical Chemistry Part C

SN - 1932-7447

IS - 15

ER -