4.8 Review

Advancing homogeneous catalysis for parahydrogen-derived hyperpolarisation and its NMR applications

Journal

CHEMICAL SCIENCE
Volume 13, Issue 17, Pages 4670-4696

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d2sc00737a

Keywords

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Funding

  1. Academy of Finland [323480]
  2. European Research Council [772110]
  3. University of Oulu (Kvantum Institute)
  4. European Research Council (ERC) [772110] Funding Source: European Research Council (ERC)
  5. Academy of Finland (AKA) [323480, 323480] Funding Source: Academy of Finland (AKA)

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Parahydrogen-induced polarisation (PHIP) is a technique that enhances nuclear magnetic resonance (NMR) signals by utilizing the chemical reactions of parahydrogen (para-H-2). Recent advances in the development of novel homogeneous catalysts have allowed for the hyperpolarisation of a wider range of target molecules. This technique has various applications in NMR reaction monitoring, mechanistic elucidation, biomedical imaging, and more.
Parahydrogen-induced polarisation (PHIP) is a nuclear spin hyperpolarisation technique employed to enhance NMR signals for a wide range of molecules. This is achieved by exploiting the chemical reactions of parahydrogen (para-H-2), the spin-0 isomer of H-2. These reactions break the molecular symmetry of para-H-2 in a way that can produce dramatically enhanced NMR signals for reaction products, and are usually catalysed by a transition metal complex. In this review, we discuss recent advances in novel homogeneous catalysts that can produce hyperpolarised products upon reaction with para-H-2. We also discuss hyperpolarisation attained in reversible reactions (termed signal amplification by reversible exchange, SABRE) and focus on catalyst developments in recent years that have allowed hyperpolarisation of a wider range of target molecules. In particular, recent examples of novel ruthenium catalysts for trans and geminal hydrogenation, metal-free catalysts, iridium sulfoxide-containing SABRE systems, and cobalt complexes for PHIP and SABRE are reviewed. Advances in this catalysis have expanded the types of molecules amenable to hyperpolarisation using PHIP and SABRE, and their applications in NMR reaction monitoring, mechanistic elucidation, biomedical imaging, and many other areas, are increasing.

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