Dagys Laurynas, Ripka Barbara, Leutzsch Markus, Moustafa Gamal A I, Eills James, Colell Johannes F P, Levitt Malcolm H
School of Chemistry, University of Southampton, Southampton SO17 1BJ, UK.
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
Magn Reson (Gott). 2020 Aug 7;1(2):175-186. doi: 10.5194/mr-1-175-2020. eCollection 2020.
In the majority of hydrogenative parahydrogen-induced polarization (PHIP) experiments, the hydrogen molecule undergoes pairwise addition to an unsaturated precursor to occupy vicinal positions on the product molecule. However, some ruthenium-based hydrogenation catalysts induce hydrogenation, leading to a reaction product in which the two hydrogen atoms are transferred to the same carbon centre, forming a methylene () group. The singlet order of parahydrogen is substantially retained over the hydrogenation reaction, giving rise to a singlet-hyperpolarized group. Although the relaxation times of the methylene protons are often short, the singlet order has a long lifetime, provided that singlet-triplet mixing is suppressed, either by chemical equivalence of the protons or by applying a resonant radiofrequency field. The long lifetime of the singlet order enables the accumulation of hyperpolarization during the slow hydrogenation reaction. We introduce a kinetic model for the behaviour of the observed hyperpolarized signals, including both the chemical kinetics and the spin dynamics of the reacting molecules. Our work demonstrates the feasibility of producing singlet-hyperpolarized methylene moieties by parahydrogen-induced polarization. This potentially extends the range of molecular agents which may be generated in a hyperpolarized state by chemical reactions of parahydrogen.
在大多数氢化仲氢诱导极化(PHIP)实验中,氢分子与不饱和前体进行成对加成,占据产物分子上的邻位。然而,一些钌基氢化催化剂会引发氢化反应,生成一种反应产物,其中两个氢原子转移到同一个碳中心,形成一个亚甲基()基团。仲氢的单重态序在氢化反应过程中基本得以保留,从而产生一个单重态超极化基团。尽管亚甲基质子的弛豫时间通常较短,但只要通过质子的化学等价性或施加共振射频场抑制单重态-三重态混合,单重态序就具有较长的寿命。单重态序的长寿命使得在缓慢的氢化反应过程中超极化得以积累。我们引入了一个动力学模型来描述所观察到的超极化信号的行为,该模型包括反应分子的化学动力学和自旋动力学。我们的工作证明了通过仲氢诱导极化产生单重态超极化亚甲基部分的可行性。这可能会扩大通过仲氢化学反应产生超极化状态的分子试剂的范围。