Activation of a catalyst [IrCl(COD)(IMes)]
(IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene;
COD = cyclooctadiene)] for signal amplification by reversible exchange
(SABRE) was monitored by in situ hyperpolarized proton
NMR at 9.4 T. During the catalyst-activation process, the COD moiety
undergoes hydrogenation that leads to its complete removal from the
Ir complex. A transient hydride intermediate of the catalyst is observed
via its hyperpolarized signatures, which could not be detected using
conventional nonhyperpolarized solution NMR. SABRE enhancement of
the pyridine substrate can be fully rendered only after removal of
the COD moiety; failure to properly activate the catalyst in the presence
of sufficient substrate can lead to irreversible deactivation consistent
with oligomerization of the catalyst molecules. Following catalyst
activation, results from selective RF-saturation studies support the
hypothesis that substrate polarization at high field arises from nuclear
cross-relaxation with hyperpolarized 1H spins of the hydride/orthohydrogen
spin bath. Importantly, the chemical changes that accompanied the
catalyst’s full activation were also found to endow the catalyst
with water solubility, here used to demonstrate SABRE hyperpolarization
of nicotinamide in water without the need for any organic cosolvent—paving
the way to various biomedical applications of SABRE hyperpolarization
methods.