Insight into catalyst speciation and hydrogen co-evolution during enantioselective formic acid-driven transfer hydrogenation with bifunctional ruthenium complexes from multi-technique operando reaction monitoring

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Abstract

Transfer hydrogenation of acetophenone from formic acid/triethylamine mixtures catalysed by the Ikariya-Noyori complex [(mesitylene)RuCl(R,R)-(TsDPEN)] has been investigated using simultaneous high-resolution FlowNMR and FlowUV-Vis spectroscopies coupled with on-line sampling head-space mass spectrometry and chiral high-performance liquid chromatography using an integrated, fully automated recirculating flow setup. In line with previous observations, the combined results show a gradual switch from formic acid dehydrogenation to hydrogen transfer mediated by the same Ru-hydride complex, and point to a Ru-formate species as the major catalyst intermediate. Hydrogen bonding in the formic acid/triethylamine mixture emerges as a sensitive 1H NMR probe for the transfer hydrogenation activity of the system and can be used to locate optimum reaction conditions.

Original languageEnglish
JournalFaraday Discussions
Early online date11 Jun 2019
DOIs
Publication statusPublished - 11 Jun 2019

Cite this

@article{7dac1113fafc47a7b37c979ec09bb328,
title = "Insight into catalyst speciation and hydrogen co-evolution during enantioselective formic acid-driven transfer hydrogenation with bifunctional ruthenium complexes from multi-technique operando reaction monitoring",
abstract = "Transfer hydrogenation of acetophenone from formic acid/triethylamine mixtures catalysed by the Ikariya-Noyori complex [(mesitylene)RuCl(R,R)-(TsDPEN)] has been investigated using simultaneous high-resolution FlowNMR and FlowUV-Vis spectroscopies coupled with on-line sampling head-space mass spectrometry and chiral high-performance liquid chromatography using an integrated, fully automated recirculating flow setup. In line with previous observations, the combined results show a gradual switch from formic acid dehydrogenation to hydrogen transfer mediated by the same Ru-hydride complex, and point to a Ru-formate species as the major catalyst intermediate. Hydrogen bonding in the formic acid/triethylamine mixture emerges as a sensitive 1H NMR probe for the transfer hydrogenation activity of the system and can be used to locate optimum reaction conditions.",
author = "Berry, {Daniel B G} and Anna Codina and Ian Clegg and Lyall, {Catherine L} and Lowe, {John P} and Ulrich Hintermair",
year = "2019",
month = "6",
day = "11",
doi = "10.1039/c9fd00060g",
language = "English",
journal = "Faraday Discussions",
issn = "1364-5498",
publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Insight into catalyst speciation and hydrogen co-evolution during enantioselective formic acid-driven transfer hydrogenation with bifunctional ruthenium complexes from multi-technique operando reaction monitoring

AU - Berry, Daniel B G

AU - Codina, Anna

AU - Clegg, Ian

AU - Lyall, Catherine L

AU - Lowe, John P

AU - Hintermair, Ulrich

PY - 2019/6/11

Y1 - 2019/6/11

N2 - Transfer hydrogenation of acetophenone from formic acid/triethylamine mixtures catalysed by the Ikariya-Noyori complex [(mesitylene)RuCl(R,R)-(TsDPEN)] has been investigated using simultaneous high-resolution FlowNMR and FlowUV-Vis spectroscopies coupled with on-line sampling head-space mass spectrometry and chiral high-performance liquid chromatography using an integrated, fully automated recirculating flow setup. In line with previous observations, the combined results show a gradual switch from formic acid dehydrogenation to hydrogen transfer mediated by the same Ru-hydride complex, and point to a Ru-formate species as the major catalyst intermediate. Hydrogen bonding in the formic acid/triethylamine mixture emerges as a sensitive 1H NMR probe for the transfer hydrogenation activity of the system and can be used to locate optimum reaction conditions.

AB - Transfer hydrogenation of acetophenone from formic acid/triethylamine mixtures catalysed by the Ikariya-Noyori complex [(mesitylene)RuCl(R,R)-(TsDPEN)] has been investigated using simultaneous high-resolution FlowNMR and FlowUV-Vis spectroscopies coupled with on-line sampling head-space mass spectrometry and chiral high-performance liquid chromatography using an integrated, fully automated recirculating flow setup. In line with previous observations, the combined results show a gradual switch from formic acid dehydrogenation to hydrogen transfer mediated by the same Ru-hydride complex, and point to a Ru-formate species as the major catalyst intermediate. Hydrogen bonding in the formic acid/triethylamine mixture emerges as a sensitive 1H NMR probe for the transfer hydrogenation activity of the system and can be used to locate optimum reaction conditions.

U2 - 10.1039/c9fd00060g

DO - 10.1039/c9fd00060g

M3 - Article

JO - Faraday Discussions

JF - Faraday Discussions

SN - 1364-5498

ER -