Parahydrogen induced
polarization (PHIP)
can address
the low sensitivity problem intrinsic to nuclear magnetic resonance
spectroscopy. Using a catalyst capable of reacting with parahydrogen and substrate in either a hydrogenative or nonhydrogenative
manner can result in signal enhancement of the substrate. This work
describes the development of a rare example of an iron catalyst capable
of reacting with parahydrogen to hyperpolarize olefins.
Complexes of the form (MesCCC)Fe(H)(L)(N2) (L
= Py (Py = pyridine), PMe3, PPh3) were synthesized
from the reaction of the parent complexes (MesCCC)FeMes(L)
(Mes = mesityl) with H2. The isolated low-spin iron(II)
hydride compounds were characterized via multinuclear NMR spectroscopy,
infrared spectroscopy, and single crystal X-ray diffraction. (MesCCC)Fe(H)(Py)(N2) is competent in the hydrogenation
of olefins and demonstrated high activity toward the hydrogenation
of monosubstituted terminal olefins. Reactions with p-H2 resulted in the first PHIP effect mediated by iron
which requires diamagnetism throughout the reaction sequence. This
work represents the development of a new PHIP catalyst featuring iron,
unlocking potential to develop more PHIP catalysts based on first-row
transition metals.