Iridium N-Heterocyclic Carbene Complexes as Efficient Catalysts for Magnetization Transfer from para-Hydrogen
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- 作者：Michael J. Cowley ; Ralph W. Adams ; Kevin D. Atkinson ; Martin C. R. Cockett ; Simon B. Duckett ; Gary G. R. Green ; Joost A. B. Lohman ; Rainer Kerssebaum ; David Kilgour ; Ryan E. Mewis
- 刊名：Journal of the American Chemical Society
- 出版年：2011
- 出版时间：April 27, 2011
- 年：2011
- 卷：133
- 期：16
- 页码：6134-6137
- 全文大小：779K
- 年卷期：v.133,no.16(April 27, 2011)
- ISSN：1520-5126
文摘
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 H2. These reversible processes bring para-H2 and py into contact in a magnetically coupled environment, delivering an 8100-fold increase in 1H 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(畏2-H2)(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.