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Iridium Cyclooctene Complex That Forms a Hyperpolarization Transfer Catalyst before Converting to a Binuclear C-H Bond Activation Product Responsible for Hydrogen Isotope Exchange.

ABSTRACT: [IrCl(COE)2]2 (1) reacts with pyridine (py) and H2 to form crystallographically characterized IrCl(H)2(COE)(py)2 (2). 2 undergoes py loss to form 16-electron IrCl(H)2(COE)(py) (3), with equivalent hydride ligands. When this reaction is studied with parahydrogen, 1 efficiently achieves hyperpolarization of free py (and nicotinamide, nicotine, 5-aminopyrimidine, and 3,5-lutudine) via signal amplification by reversible exchange (SABRE) and hence reflects a simple and readily available precatayst for this process. 2 reacts further over 48 h at 298 K to form crystallographically characterized (Cl)(H)(py)(?-Cl)(?-H)(?-?-NC5H4)Ir(H)(py)2 (4). This dimer is active in the hydrogen isotope exchange process that is used in radiopharmaceutical preparations. Furthermore, while [Ir(H)2(COE)(py)3]PF6 (6) forms upon the addition of AgPF6 to 2, its stability precludes its efficient involvement in SABRE.

SUBMITTER: Iali W 

PROVIDER: S-EPMC5193467 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature

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Iridium Cyclooctene Complex That Forms a Hyperpolarization Transfer Catalyst before Converting to a Binuclear C-H Bond Activation Product Responsible for Hydrogen Isotope Exchange.

Iali Wissam W   Green Gary G R GG   Hart Sam J SJ   Whitwood Adrian C AC   Duckett Simon B SB  

Inorganic chemistry 20161109 22

[IrCl(COE)<sub>2</sub>]<sub>2</sub> (1) reacts with pyridine (py) and H<sub>2</sub> to form crystallographically characterized IrCl(H)<sub>2</sub>(COE)(py)<sub>2</sub> (2). 2 undergoes py loss to form 16-electron IrCl(H)<sub>2</sub>(COE)(py) (3), with equivalent hydride ligands. When this reaction is studied with parahydrogen, 1 efficiently achieves hyperpolarization of free py (and nicotinamide, nicotine, 5-aminopyrimidine, and 3,5-lutudine) via signal amplification by reversible exchange (SABR  ...[more]

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