Issue 4, 2023

Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand

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.

Graphical abstract: Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand

Supplementary files

Article information

Article type
Paper
Submitted
09 Nov 2022
Accepted
20 Dec 2022
First published
21 Dec 2022
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2023,52, 1096-1104

Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand

E. W. Poole, I. Bustos, T. M. Hood, J. E. Smart and A. B. Chaplin, Dalton Trans., 2023, 52, 1096 DOI: 10.1039/D2DT03608H

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