Probing the carbon-hydrogen activation of alkanes following photolysis of Tp′Rh(CNR)(carbodiimide): A computational and time-resolved infrared spectroscopic study

Jia Guan, Alisdair Wriglesworth, Xue Zhong Sun, Edward Brothers, Snežana D. Zarić, Meagan E. Evans, William D. Jones, Michael Towrie, Michael B. Hall, Michael W. George

Research output: Contribution to journalArticle

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Abstract

Carbon-hydrogen bond activation of alkanes by Tp′Rh(CNR) (Tp′ = Tp = trispyrazolylborate or Tp∗ = tris(3,5-dimethylpyrazolyl)borate) were followed by time-resolved infrared spectroscopy (TRIR) in the v(CNR) and v (B-H) spectral regions on TpRh(CNCH2CMe3), and their reaction mechanisms were modeled by density functional theory (DFT) on TpRh(CNMe). The major intermediate species were: κ31-alkane complex (1); κ22-alkane complex (2); and κ3-alkyl hydride (3). Calculations predict that the barrier between 1 and 2 arises from a triplet-singlet crossing and intermediate 2 proceeds over the rate-determining C-H activation barrier to give the final product 3. The activation lifetimes measured for the TpRh(CNR) and TpRh(CO) fragments with n-heptane and four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) increase with alkanes size and show a dramatic increase between C6H12 and C7H14. A similar step-like behavior was observed previously with CpRh(CO) and CpRh(CO) fragments and is attributed to the wider difference in C-H bonds that appear at C7H14. However, Tp′Rh(CNR) and Tp′Rh(CO) fragments have much longer absolute lifetimes compared to those of CpRh(CO) and CpRh(CO) fragments, because the reduced electron density in dechelated κ22-alkane Tp′ complexes stabilizes the d8 Rh(I) in a square-planar geometry and weakens the metal′s ability for oxidative addition of the C-H bond. Further, the Tp′Rh(CNR) fragment has significantly slower rates of C-H activation in comparison to the Tp′Rh(CO) fragment for the larger cycloalkanes, because the steric bulk of the neopentyl isocyanide ligand hinders the rechelation in κ2-Tp′Rh(CNR)(cycloalkane) species and results in the C-H activation without the assistance of the rechelation.

Original languageEnglish
Pages (from-to)1842-1854
Number of pages13
JournalJournal of the American Chemical Society
Volume140
Issue number5
DOIs
Publication statusPublished - 7 Feb 2018

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Carbodiimides
Alkanes
Photolysis
Carbon Monoxide
Paraffins
Hydrogen
Carbon
Chemical activation
Infrared radiation
Cycloparaffins
Heptane
Hydrides
Density functional theory
Carrier concentration
Borates
Infrared spectroscopy
Hydrogen bonds
Cyanides
Ligands
Spectrum Analysis

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Probing the carbon-hydrogen activation of alkanes following photolysis of Tp′Rh(CNR)(carbodiimide) : A computational and time-resolved infrared spectroscopic study. / Guan, Jia; Wriglesworth, Alisdair; Sun, Xue Zhong; Brothers, Edward; Zarić, Snežana D.; Evans, Meagan E.; Jones, William D.; Towrie, Michael; Hall, Michael B.; George, Michael W.

In: Journal of the American Chemical Society, Vol. 140, No. 5, 07.02.2018, p. 1842-1854.

Research output: Contribution to journalArticle

Guan, Jia ; Wriglesworth, Alisdair ; Sun, Xue Zhong ; Brothers, Edward ; Zarić, Snežana D. ; Evans, Meagan E. ; Jones, William D. ; Towrie, Michael ; Hall, Michael B. ; George, Michael W. / Probing the carbon-hydrogen activation of alkanes following photolysis of Tp′Rh(CNR)(carbodiimide) : A computational and time-resolved infrared spectroscopic study. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 5. pp. 1842-1854.
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abstract = "Carbon-hydrogen bond activation of alkanes by Tp′Rh(CNR) (Tp′ = Tp = trispyrazolylborate or Tp∗ = tris(3,5-dimethylpyrazolyl)borate) were followed by time-resolved infrared spectroscopy (TRIR) in the v(CNR) and v (B-H) spectral regions on TpRh(CNCH2CMe3), and their reaction mechanisms were modeled by density functional theory (DFT) on TpRh(CNMe). The major intermediate species were: κ3-ν1-alkane complex (1); κ2-ν2-alkane complex (2); and κ3-alkyl hydride (3). Calculations predict that the barrier between 1 and 2 arises from a triplet-singlet crossing and intermediate 2 proceeds over the rate-determining C-H activation barrier to give the final product 3. The activation lifetimes measured for the TpRh(CNR) and TpRh(CO) fragments with n-heptane and four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) increase with alkanes size and show a dramatic increase between C6H12 and C7H14. A similar step-like behavior was observed previously with CpRh(CO) and CpRh(CO) fragments and is attributed to the wider difference in C-H bonds that appear at C7H14. However, Tp′Rh(CNR) and Tp′Rh(CO) fragments have much longer absolute lifetimes compared to those of CpRh(CO) and CpRh(CO) fragments, because the reduced electron density in dechelated κ2-ν2-alkane Tp′ complexes stabilizes the d8 Rh(I) in a square-planar geometry and weakens the metal′s ability for oxidative addition of the C-H bond. Further, the Tp′Rh(CNR) fragment has significantly slower rates of C-H activation in comparison to the Tp′Rh(CO) fragment for the larger cycloalkanes, because the steric bulk of the neopentyl isocyanide ligand hinders the rechelation in κ2-Tp′Rh(CNR)(cycloalkane) species and results in the C-H activation without the assistance of the rechelation.",
author = "Jia Guan and Alisdair Wriglesworth and Sun, {Xue Zhong} and Edward Brothers and Zarić, {Snežana D.} and Evans, {Meagan E.} and Jones, {William D.} and Michael Towrie and Hall, {Michael B.} and George, {Michael W.}",
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T2 - A computational and time-resolved infrared spectroscopic study

AU - Guan, Jia

AU - Wriglesworth, Alisdair

AU - Sun, Xue Zhong

AU - Brothers, Edward

AU - Zarić, Snežana D.

AU - Evans, Meagan E.

AU - Jones, William D.

AU - Towrie, Michael

AU - Hall, Michael B.

AU - George, Michael W.

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N2 - Carbon-hydrogen bond activation of alkanes by Tp′Rh(CNR) (Tp′ = Tp = trispyrazolylborate or Tp∗ = tris(3,5-dimethylpyrazolyl)borate) were followed by time-resolved infrared spectroscopy (TRIR) in the v(CNR) and v (B-H) spectral regions on TpRh(CNCH2CMe3), and their reaction mechanisms were modeled by density functional theory (DFT) on TpRh(CNMe). The major intermediate species were: κ3-ν1-alkane complex (1); κ2-ν2-alkane complex (2); and κ3-alkyl hydride (3). Calculations predict that the barrier between 1 and 2 arises from a triplet-singlet crossing and intermediate 2 proceeds over the rate-determining C-H activation barrier to give the final product 3. The activation lifetimes measured for the TpRh(CNR) and TpRh(CO) fragments with n-heptane and four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) increase with alkanes size and show a dramatic increase between C6H12 and C7H14. A similar step-like behavior was observed previously with CpRh(CO) and CpRh(CO) fragments and is attributed to the wider difference in C-H bonds that appear at C7H14. However, Tp′Rh(CNR) and Tp′Rh(CO) fragments have much longer absolute lifetimes compared to those of CpRh(CO) and CpRh(CO) fragments, because the reduced electron density in dechelated κ2-ν2-alkane Tp′ complexes stabilizes the d8 Rh(I) in a square-planar geometry and weakens the metal′s ability for oxidative addition of the C-H bond. Further, the Tp′Rh(CNR) fragment has significantly slower rates of C-H activation in comparison to the Tp′Rh(CO) fragment for the larger cycloalkanes, because the steric bulk of the neopentyl isocyanide ligand hinders the rechelation in κ2-Tp′Rh(CNR)(cycloalkane) species and results in the C-H activation without the assistance of the rechelation.

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