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Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand
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Poole, E. W., Bustos, I., Hood, Thomas M., Smart, J. E. and Chaplin, Adrian B. (2023) Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand. Dalton Transactions, 52 (4). pp. 1096-1104. doi:10.1039/D2DT03608H ISSN 1477-9226.
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Official URL: https://doi.org/10.1039/D2DT03608H
Abstract
The synthesis and iridium coordination chemistry of a new pyridine-based phosphinito pincer ligand 2,6-(ArF2PO)2C5H3N (PONOP-ArF; ArF = 2-(CF3)C6H4) are described, where the P-donors have ortho-trifluoromethylphenyl substituents. The iridium(III) 2,2′-biphenyl (biph) derivative [Ir(PONOP-ArF)(biph)Cl] was obtained by reaction with [Ir(biph)(COD)Cl]2 (COD = 1,5-cyclooctadiene) and subsequent halide ion abstraction enabled isolation of [Ir(PONOP-ArF)(biph)]+ which features an Ir ← F–C bonding interaction in the solid state. Hydrogenolysis of the biphenyl ligand and formation of [Ir(PONOP-ArF)(H)2]+ was achieved by prolonged reaction of [Ir(PONOP-ArF)(biph)]+ with dihydrogen. This transformation paved the way for isolation and crystallographic characterisation of low valent iridium derivatives through treatment of the dihydride with tert-butylethylene (TBE). The iridium(I) π-complex [Ir(PONOP-ArF)(TBE)]+ is thermally stable but substitution of TBE can be achieved by reaction with carbon monoxide. The solid-state structure of the mono-carbonyl product [Ir(PONOP-ArF)(CO)]+ is notable for an intermolecular anagostic interaction between the metal centre and a pentane molecule which co-crystallises within a cleft defined by two aryl phosphine substituents.
Item Type: | Journal Article | |||||||||||||||||||||||||||
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Subjects: | Q Science > QD Chemistry | |||||||||||||||||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | |||||||||||||||||||||||||||
Library of Congress Subject Headings (LCSH): | Iridium , Iridium compounds, Organofluorine compounds , Organometallic compounds | |||||||||||||||||||||||||||
Journal or Publication Title: | Dalton Transactions | |||||||||||||||||||||||||||
Publisher: | Royal Society of Chemistry | |||||||||||||||||||||||||||
ISSN: | 1477-9226 | |||||||||||||||||||||||||||
Official Date: | 28 January 2023 | |||||||||||||||||||||||||||
Dates: |
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Volume: | 52 | |||||||||||||||||||||||||||
Number: | 4 | |||||||||||||||||||||||||||
Page Range: | pp. 1096-1104 | |||||||||||||||||||||||||||
DOI: | 10.1039/D2DT03608H | |||||||||||||||||||||||||||
Status: | Peer Reviewed | |||||||||||||||||||||||||||
Publication Status: | Published | |||||||||||||||||||||||||||
Access rights to Published version: | Restricted or Subscription Access | |||||||||||||||||||||||||||
Date of first compliant deposit: | 20 December 2022 | |||||||||||||||||||||||||||
Date of first compliant Open Access: | 20 February 2023 | |||||||||||||||||||||||||||
RIOXX Funder/Project Grant: |
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