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
Pages (from-to)45-57
JournalFaraday Discussions
Volume220
Early online date11 Jun 2019
DOIs
Publication statusPublished - 11 Jun 2019

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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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",
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journal = "Faraday Discussions",
issn = "1364-5498",
publisher = "Royal Society of Chemistry",

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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.

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