Catalytic Alkane Transfer Dehydrogenation by PSP-Pincer-Ligated Ruthenium. Deactivation of an Extremely Reactive Fragment by Formation of Allyl Hydride Complexes

Xiaoguang Zhou, Santanu Malakar, Tian Zhou, Sathiyamoorthy Murugesan, Carlos Huang, Thomas J. Emge, Karsten Krogh-Jespersen, Alan S Goldman

Research output: Contribution to journalArticle

Abstract

Iridium complexes bearing PCP-type pincer ligands are the most effective catalysts reported to date for the low-temperature (≤ca. 200 °C) dehydrogenation of alkanes. To investigate the activity of formally isoelectronic ruthenium complexes, we have synthesized the neutral 2,7-di-tert-butyl-4,5-bis(diisopropylphosphino)-9,9-dimethylthioxanthene ( iPr xanPSP) pincer ligand and several Ru complexes thereof. The ( iPr xanPSP)Ru complexes catalyze alkane transfer dehydrogenation of the benchmark cyclooctane/t-butylethylene (COA/TBE) couple with turnover frequencies up to ca. 1 s -1 at 150 °C and 0.2 s -1 at 120 °C, the highest rates for alkane dehydrogenation ever reported at such temperatures. Dehydrogenation of n-octane, however, is much less effective. A combination of experiment and DFT calculations allow us to explain why ( iPr xanPSP)Ru is more effective than ( iPr PCP)Ir for dehydrogenation of COA, while the reverse is true for dehydrogenation of n-alkanes. Considering only in-cycle species and simple olefin complexes, the ( iPr xanPSP)Ru fragment is calculated to be much more active than ( iPr PCP)Ir for dehydrogenation of both COA and n-alkanes. However, the resting state in the ( iPr xanPSP)Ru-catalyzed transfer dehydrogenation of n-alkane is a very stable linear-allyl hydride complex, whereas the corresponding cyclooctenyl hydride is much less stable.

Original languageEnglish
Pages (from-to)4072-4083
Number of pages12
JournalACS Catalysis
DOIs
Publication statusPublished - Jan 1 2019

Fingerprint

Alkanes
Ruthenium
Dehydrogenation
Hydrides
Paraffins
Bearings (structural)
Ligands
Iridium
Alkenes
Discrete Fourier transforms
Olefins
Temperature
Catalysts

Keywords

  • alkane dehydrogenation
  • allyl complexes
  • catalyst deactivation
  • pincer ligand
  • ruthenium

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Catalytic Alkane Transfer Dehydrogenation by PSP-Pincer-Ligated Ruthenium. Deactivation of an Extremely Reactive Fragment by Formation of Allyl Hydride Complexes. / Zhou, Xiaoguang; Malakar, Santanu; Zhou, Tian; Murugesan, Sathiyamoorthy; Huang, Carlos; Emge, Thomas J.; Krogh-Jespersen, Karsten; Goldman, Alan S.

In: ACS Catalysis, 01.01.2019, p. 4072-4083.

Research output: Contribution to journalArticle

Zhou, Xiaoguang ; Malakar, Santanu ; Zhou, Tian ; Murugesan, Sathiyamoorthy ; Huang, Carlos ; Emge, Thomas J. ; Krogh-Jespersen, Karsten ; Goldman, Alan S. / Catalytic Alkane Transfer Dehydrogenation by PSP-Pincer-Ligated Ruthenium. Deactivation of an Extremely Reactive Fragment by Formation of Allyl Hydride Complexes. In: ACS Catalysis. 2019 ; pp. 4072-4083.
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abstract = "Iridium complexes bearing PCP-type pincer ligands are the most effective catalysts reported to date for the low-temperature (≤ca. 200 °C) dehydrogenation of alkanes. To investigate the activity of formally isoelectronic ruthenium complexes, we have synthesized the neutral 2,7-di-tert-butyl-4,5-bis(diisopropylphosphino)-9,9-dimethylthioxanthene ( iPr xanPSP) pincer ligand and several Ru complexes thereof. The ( iPr xanPSP)Ru complexes catalyze alkane transfer dehydrogenation of the benchmark cyclooctane/t-butylethylene (COA/TBE) couple with turnover frequencies up to ca. 1 s -1 at 150 °C and 0.2 s -1 at 120 °C, the highest rates for alkane dehydrogenation ever reported at such temperatures. Dehydrogenation of n-octane, however, is much less effective. A combination of experiment and DFT calculations allow us to explain why ( iPr xanPSP)Ru is more effective than ( iPr PCP)Ir for dehydrogenation of COA, while the reverse is true for dehydrogenation of n-alkanes. Considering only in-cycle species and simple olefin complexes, the ( iPr xanPSP)Ru fragment is calculated to be much more active than ( iPr PCP)Ir for dehydrogenation of both COA and n-alkanes. However, the resting state in the ( iPr xanPSP)Ru-catalyzed transfer dehydrogenation of n-alkane is a very stable linear-allyl hydride complex, whereas the corresponding cyclooctenyl hydride is much less stable.",
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AU - Malakar, Santanu

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AU - Murugesan, Sathiyamoorthy

AU - Huang, Carlos

AU - Emge, Thomas J.

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AB - Iridium complexes bearing PCP-type pincer ligands are the most effective catalysts reported to date for the low-temperature (≤ca. 200 °C) dehydrogenation of alkanes. To investigate the activity of formally isoelectronic ruthenium complexes, we have synthesized the neutral 2,7-di-tert-butyl-4,5-bis(diisopropylphosphino)-9,9-dimethylthioxanthene ( iPr xanPSP) pincer ligand and several Ru complexes thereof. The ( iPr xanPSP)Ru complexes catalyze alkane transfer dehydrogenation of the benchmark cyclooctane/t-butylethylene (COA/TBE) couple with turnover frequencies up to ca. 1 s -1 at 150 °C and 0.2 s -1 at 120 °C, the highest rates for alkane dehydrogenation ever reported at such temperatures. Dehydrogenation of n-octane, however, is much less effective. A combination of experiment and DFT calculations allow us to explain why ( iPr xanPSP)Ru is more effective than ( iPr PCP)Ir for dehydrogenation of COA, while the reverse is true for dehydrogenation of n-alkanes. Considering only in-cycle species and simple olefin complexes, the ( iPr xanPSP)Ru fragment is calculated to be much more active than ( iPr PCP)Ir for dehydrogenation of both COA and n-alkanes. However, the resting state in the ( iPr xanPSP)Ru-catalyzed transfer dehydrogenation of n-alkane is a very stable linear-allyl hydride complex, whereas the corresponding cyclooctenyl hydride is much less stable.

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