Richards, Josh E., Hooper, Alexander J.J., Bayfield, Oliver W. et al. (9 more authors) (2018) Using hyperpolarised NMR and DFT to rationalise the unexpected hydrogenation of quinazoline to 3,4-dihydroquinazoline. Chemical Communications. pp. 10375-10378. ISSN 1364-548X
Abstract
PHIP and SABRE hyperpolarized NMR methods are used to follow the unexpected metal-catalysed hydrogenation of quinazoline (Qu) to 3,4-dihydroquinazoline as the sole product. A solution of [IrCl(IMes)(COD)] in dichloromethane reacts with H2 and Qu to form [IrCl(H)2(IMes)(Qu)2] (2). The addition of methanol then results in its conversion to [Ir(H)2(IMes)(Qu)3]Cl (3) which catalyses the hydrogenation reaction. Density functional theory calculations are used to rationalise a proposed outer sphere mechanism in which (3) converts to [IrCl(H)2(H2)(IMes)(Qu)2]Cl (4) and neutral [Ir(H)3(IMes)(Qu)2] (6), both of which are involved in the formation of 3,4-dihydroquinazoline via the stepwise transfer of H+ and H−, with H2 identified as the reductant. Successive ligand exchange in 3 results in the production of thermodynamically stable [Ir(H)2(IMes)(3,4-dihydroquinazoline)3]Cl (5).
Metadata
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Copyright, Publisher and Additional Information: | © The Royal Society of Chemistry 2018. | ||||
Dates: |
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Institution: | The University of York | ||||
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) | ||||
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Depositing User: | Pure (York) | ||||
Date Deposited: | 06 Sep 2018 15:30 | ||||
Last Modified: | 04 Feb 2024 00:56 | ||||
Published Version: | https://doi.org/10.1039/C8CC04826F | ||||
Status: | Published | ||||
Refereed: | Yes | ||||
Identification Number: | https://doi.org/10.1039/C8CC04826F | ||||
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