Iridium N-Heterocyclic Carbene Complexes as Efficient Catalysts for Magnetization Transfer from <i>para</i>-Hydrogen

TLDR

NMR spectroscopy is crucial for material characterization and medical imaging, yet its inherently low sensitivity limits its utility. The Ir(I) N‑heterocyclic carbene complex undergoes reversible pyridine loss and H₂ reductive elimination, creating a magnetically coupled environment that transfers para‑H₂ magnetization to py; DFT studies identify a key [Ir(H)₂(η²‑H₂)(IMes)(py)₂]⁺ intermediate and show the transfer efficiency depends on the magnetic field strength. Using this catalyst, the authors achieved an 8,100‑fold increase in ¹H NMR signal of py at 3 T, and deuterium labeling further improved the signal by 60 %.

Abstract

While the characterization of materials by NMR is hugely important in the physical and biological sciences, it also plays a vital role in medical imaging. This success is all the more impressive because of the inherently low sensitivity of the method. We establish here that [Ir(H)(2)(IMes)(py)(3)]Cl undergoes both pyridine (py) loss as well as the reductive elimination of H(2). These reversible processes bring para-H(2) and py into contact in a magnetically coupled environment, delivering an 8100-fold increase in (1)H NMR signal strength relative to non-hyperpolarized py at 3 T. An apparatus that facilitates signal averaging has been built to demonstrate that the efficiency of this process is controlled by the strength of the magnetic field experienced by the complex during the magnetization transfer step. Thermodynamic and kinetic data combined with DFT calculations reveal the involvement of [Ir(H)(2)(η(2)-H(2))(IMes)(py)(2)](+), an unlikely yet key intermediate in the reaction. Deuterium labeling yields an additional 60% improvement in signal, an observation that offers insight into strategies for optimizing this approach.