Spontaneous transfer of Parahydrogen derived spin order to pyridine at low magnetic field

Kevin D. Atkinson, Michael J. Cowley, Paul I P Elliott, Simon B. Duckett, Gary G R Green, Joaquín López-Serrano, Adrian C. Whitwood

Research output: Contribution to journalArticle

112 Citations (Scopus)

Abstract

The cationic iridium complex [Ir(COD)(PCy3)(py)]BF4 (1) is shown to react with dihydrogen in the presence of pyridine (py) to form the dihydride complex fac,cis-[Ir(PCy3)(py)3(H) 2]BF4 (2). Complex 2 undergoes rapid exchange of the two bound pyridine ligands which are trans to hydride with free pyridine; the activation parameters for this process in methanol are ΔH‡ = 97.4 ± 9 kJ mol-1 and ΔS‡ = 84 ( 31 J K-1 mol-1. When parahydrogen is employed as a source of nuclear spin polarization, spontaneous magnetization transfer proceeds in low magnetic field from the two nascent hydride ligands of 2 to its other NMR active nuclei. Upon interrogation by NMR spectroscopy in a second step, signal enhancements in excess of 100 fold are observed for the 1H, 13C and 15N resonances of free pyridine after ligand exchange. The degree of signal enhancement in the free substrate is increased by employing electronically rich and sterically encumbered phosphine ligands such as PCy 3, PCy2Ph, or PiPr3 and by optimizing the strength of the magnetic field in which polarization transfer occurs.

LanguageEnglish
Pages13362-13368
Number of pages7
JournalJournal of the American Chemical Society
Volume131
Issue number37
DOIs
Publication statusPublished - 23 Sep 2009
Externally publishedYes

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Magnetic Fields
Pyridine
Ligands
Magnetic fields
phosphine
Hydrides
Iridium
Spin polarization
Nuclear magnetic resonance spectroscopy
Methanol
Magnetization
Magnetic Resonance Spectroscopy
Chemical activation
Nuclear magnetic resonance
Polarization
pyridine
Substrates

Cite this

Atkinson, K. D., Cowley, M. J., Elliott, P. I. P., Duckett, S. B., Green, G. G. R., López-Serrano, J., & Whitwood, A. C. (2009). Spontaneous transfer of Parahydrogen derived spin order to pyridine at low magnetic field. Journal of the American Chemical Society, 131(37), 13362-13368. https://doi.org/10.1021/ja903601p
Atkinson, Kevin D. ; Cowley, Michael J. ; Elliott, Paul I P ; Duckett, Simon B. ; Green, Gary G R ; López-Serrano, Joaquín ; Whitwood, Adrian C. / Spontaneous transfer of Parahydrogen derived spin order to pyridine at low magnetic field. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 37. pp. 13362-13368.
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abstract = "The cationic iridium complex [Ir(COD)(PCy3)(py)]BF4 (1) is shown to react with dihydrogen in the presence of pyridine (py) to form the dihydride complex fac,cis-[Ir(PCy3)(py)3(H) 2]BF4 (2). Complex 2 undergoes rapid exchange of the two bound pyridine ligands which are trans to hydride with free pyridine; the activation parameters for this process in methanol are ΔH‡ = 97.4 ± 9 kJ mol-1 and ΔS‡ = 84 ( 31 J K-1 mol-1. When parahydrogen is employed as a source of nuclear spin polarization, spontaneous magnetization transfer proceeds in low magnetic field from the two nascent hydride ligands of 2 to its other NMR active nuclei. Upon interrogation by NMR spectroscopy in a second step, signal enhancements in excess of 100 fold are observed for the 1H, 13C and 15N resonances of free pyridine after ligand exchange. The degree of signal enhancement in the free substrate is increased by employing electronically rich and sterically encumbered phosphine ligands such as PCy 3, PCy2Ph, or PiPr3 and by optimizing the strength of the magnetic field in which polarization transfer occurs.",
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Atkinson, KD, Cowley, MJ, Elliott, PIP, Duckett, SB, Green, GGR, López-Serrano, J & Whitwood, AC 2009, 'Spontaneous transfer of Parahydrogen derived spin order to pyridine at low magnetic field', Journal of the American Chemical Society, vol. 131, no. 37, pp. 13362-13368. https://doi.org/10.1021/ja903601p

Spontaneous transfer of Parahydrogen derived spin order to pyridine at low magnetic field. / Atkinson, Kevin D.; Cowley, Michael J.; Elliott, Paul I P; Duckett, Simon B.; Green, Gary G R; López-Serrano, Joaquín; Whitwood, Adrian C.

In: Journal of the American Chemical Society, Vol. 131, No. 37, 23.09.2009, p. 13362-13368.

Research output: Contribution to journalArticle

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N2 - The cationic iridium complex [Ir(COD)(PCy3)(py)]BF4 (1) is shown to react with dihydrogen in the presence of pyridine (py) to form the dihydride complex fac,cis-[Ir(PCy3)(py)3(H) 2]BF4 (2). Complex 2 undergoes rapid exchange of the two bound pyridine ligands which are trans to hydride with free pyridine; the activation parameters for this process in methanol are ΔH‡ = 97.4 ± 9 kJ mol-1 and ΔS‡ = 84 ( 31 J K-1 mol-1. When parahydrogen is employed as a source of nuclear spin polarization, spontaneous magnetization transfer proceeds in low magnetic field from the two nascent hydride ligands of 2 to its other NMR active nuclei. Upon interrogation by NMR spectroscopy in a second step, signal enhancements in excess of 100 fold are observed for the 1H, 13C and 15N resonances of free pyridine after ligand exchange. The degree of signal enhancement in the free substrate is increased by employing electronically rich and sterically encumbered phosphine ligands such as PCy 3, PCy2Ph, or PiPr3 and by optimizing the strength of the magnetic field in which polarization transfer occurs.

AB - The cationic iridium complex [Ir(COD)(PCy3)(py)]BF4 (1) is shown to react with dihydrogen in the presence of pyridine (py) to form the dihydride complex fac,cis-[Ir(PCy3)(py)3(H) 2]BF4 (2). Complex 2 undergoes rapid exchange of the two bound pyridine ligands which are trans to hydride with free pyridine; the activation parameters for this process in methanol are ΔH‡ = 97.4 ± 9 kJ mol-1 and ΔS‡ = 84 ( 31 J K-1 mol-1. When parahydrogen is employed as a source of nuclear spin polarization, spontaneous magnetization transfer proceeds in low magnetic field from the two nascent hydride ligands of 2 to its other NMR active nuclei. Upon interrogation by NMR spectroscopy in a second step, signal enhancements in excess of 100 fold are observed for the 1H, 13C and 15N resonances of free pyridine after ligand exchange. The degree of signal enhancement in the free substrate is increased by employing electronically rich and sterically encumbered phosphine ligands such as PCy 3, PCy2Ph, or PiPr3 and by optimizing the strength of the magnetic field in which polarization transfer occurs.

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