title: Iridium N-heterocyclic carbene complexes as efficient catalysts for magnetization transfer from para-hydrogen.
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.
authors.affiliation: Department of Chemistry, University of York, Heslington, York YO10 5DD, UK.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Cowley
authors.forename: Ralph W
authors.initials: RW
authors.lastname: Adams
authors.forename: Kevin D
authors.initials: KD
authors.lastname: Atkinson
authors.forename: Martin C R
authors.initials: MC
authors.lastname: Cockett
authors.forename: Simon B
authors.initials: SB
authors.lastname: Duckett
authors.forename: Gary G R
authors.initials: GG
authors.lastname: Green
authors.forename: Joost A B
authors.initials: JA
authors.lastname: Lohman
authors.forename: Rainer
authors.initials: R
authors.lastname: Kerssebaum
authors.forename: David
authors.initials: D
authors.lastname: Kilgour
authors.forename: Ryan E
authors.initials: RE
authors.lastname: Mewis
mesh_terms: D002384:Catalysis; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008280:Magnetics; D008958:Models, Molecular
chemical_list: D006571:Heterocyclic Compounds; D007495:Iridium; D006859:Hydrogen