Reaction monitoring using SABRE-hyperpolarized benchtop (1 T) NMR spectroscopy

Olga Semenova, Peter Michael Richardson, Andrew Parrott, Alison Nordon, Meghan Eileen Halse, Simon Duckett

Research output: Contribution to journalArticlepeer-review


The conversion of [IrCl(COD)(IMes)] (COD = cis,cis-1,5-cyclooctadiene, IMes = 1,3-bis(2,4,6-trimethyl-phenyl)imidazole-2-ylidene) in the presence of an excess of p-H2 and a substrate (4-aminopyridine (4-AP) or 4-methylpyridine (4-MP)) into [Ir(H)2(IMes)(substrate)3]Cl is monitored by 1H NMR spectroscopy using a benchtop (1 T) spectrometer in conjunction with the parahydrogen (p-H2) based hyperpolarization technique signal amplification by reversible exchange (SABRE). A series of single-shot 1H NMR measurements are used to monitor the chemical changes that take place in solution through the lifetime of the hyperpolarized response. Non-hyperpolarized high-field 1H NMR control measurements were also undertaken to confirm that the observed time dependent changes relate directly to the underlying chemical evolution. The formation of [Ir(H)2(IMes)(substrate)3]Cl is further linked to the hydrogen isotope exchange reaction (HIE) which leads to the incorporation of deuterium into the ortho positions of 4-AP, where the source of deuterium is the solvent, methanol-d4. Comparable reaction monitoring results are achieved at both high-field (9.4 T) and low-field (1 T). It is notable, that the low sensitivity of the benchtop (1 T) NMR enables the use of protio solvents, which is harnessed here to separate the effects of catalyst formation and substrate deuteration. Collectively, these methods illustrate how low-cost low-field NMR measurements provide unique insight into a complex catalytic process through a combination of hyperpolarization and relaxation data.
Original languageEnglish
Article number9b00729
Pages (from-to)6695-6701
Number of pages7
JournalAnalytical Chemistry
Issue number10
Early online date15 Apr 2019
Publication statusPublished - 21 May 2019

Bibliographical note

© 2019 American Chemical Society.

Cite this