Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand

The synthesis and iridium coordination chemistry of a new pyridine-based phosphinito pincer ligand 2,6-(Ar^F₂PO)₂C₅H₃N (PONOP-Ar^F; Ar^F = 2-(CF₃)C₆H₄) are described, where the P-donors have ortho-trifluoromethylphenyl substituents. The iridium(III) 2,2'-biphenyl (biph) derivative [Ir(PONOP-Ar^F)(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-Ar^F)(biph)]⁺ which features an Ir ← F-C bonding interaction in the solid state. Hydrogenolysis of the biphenyl ligand and formation of [Ir(PONOP-Ar^F)(H)₂]⁺ was achieved by prolonged reaction of [Ir(PONOP-Ar^F)(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-Ar^F)(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-Ar^F)(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.