Iridium cyclooctene complex that forms a hyperpolarization transfer catalyst before converting to a binuclear C-H bond activation product responsible for hydrogen isotope exchange

Wissam Iali; Gary G.R. Green; Sam J. Hart; Adrian C. Whitwood; Simon B. Duckett

doi:10.1021/acs.inorgchem.6b02560

Iridium cyclooctene complex that forms a hyperpolarization transfer catalyst before converting to a binuclear C-H bond activation product responsible for hydrogen isotope exchange

Wissam Iali
, Gary G.R. Green
, Sam J. Hart
, Adrian C. Whitwood
, Simon B. Duckett^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

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)(μ-Cl)(μ-H)(κ-μ-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.

Original language	English
Pages (from-to)	11639-11643
Number of pages	5
Journal	Inorganic Chemistry
Volume	55
Issue number	22
DOIs	https://doi.org/10.1021/acs.inorgchem.6b02560
State	Published - 21 Nov 2016
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.6b02560

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@article{1f88bfafa1ad452c95a3ff65f74f8d38,

title = "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)(μ-Cl)(μ-H)(κ-μ-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.",

author = "Wissam Iali and Green, \{Gary G.R.\} and Hart, \{Sam J.\} and Whitwood, \{Adrian C.\} and Duckett, \{Simon B.\}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = nov,

day = "21",

doi = "10.1021/acs.inorgchem.6b02560",

language = "English",

volume = "55",

pages = "11639--11643",

journal = "Inorganic Chemistry",

issn = "0020-1669",

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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; Green, Gary G.R.; Hart, Sam J. et al.
In: Inorganic Chemistry, Vol. 55, No. 22, 21.11.2016, p. 11639-11643.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Iridium cyclooctene complex that forms a hyperpolarization transfer catalyst before converting to a binuclear C-H bond activation product responsible for hydrogen isotope exchange

AU - Iali, Wissam

AU - Green, Gary G.R.

AU - Hart, Sam J.

AU - Whitwood, Adrian C.

AU - Duckett, Simon B.

PY - 2016/11/21

Y1 - 2016/11/21

N2 - [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)(μ-Cl)(μ-H)(κ-μ-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.

AB - [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)(μ-Cl)(μ-H)(κ-μ-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.

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U2 - 10.1021/acs.inorgchem.6b02560

DO - 10.1021/acs.inorgchem.6b02560

M3 - Article

AN - SCOPUS:84997824543

SN - 0020-1669

VL - 55

SP - 11639

EP - 11643

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 22

ER -

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

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