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

doi:10.1021/ja903601p

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 journal › Article › peer-review

153 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.

Original language	English
Pages (from-to)	13362-13368
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	131
Issue number	37
DOIs	https://doi.org/10.1021/ja903601p
Publication status	Published - 23 Sep 2009
Externally published	Yes

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@article{5773e4212d72477bb84db081560f21cc,

title = "Spontaneous transfer of Parahydrogen derived spin order to pyridine at low magnetic field",

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.",

author = "Atkinson, {Kevin D.} and Cowley, {Michael J.} and Elliott, {Paul I P} and Duckett, {Simon B.} and Green, {Gary G R} and Joaqu{\'i}n L{\'o}pez-Serrano and Whitwood, {Adrian C.}",

year = "2009",

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doi = "10.1021/ja903601p",

language = "English",

volume = "131",

pages = "13362--13368",

journal = "Journal of the American Chemical Society",

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T1 - Spontaneous transfer of Parahydrogen derived spin order to pyridine at low magnetic field

AU - Atkinson, Kevin D.

AU - Cowley, Michael J.

AU - Elliott, Paul I P

AU - Duckett, Simon B.

AU - Green, Gary G R

AU - López-Serrano, Joaquín

AU - Whitwood, Adrian C.

PY - 2009/9/23

Y1 - 2009/9/23

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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U2 - 10.1021/ja903601p

DO - 10.1021/ja903601p

M3 - Article

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VL - 131

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

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ER -

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

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