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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(F)(2)PO)(2)C(5)H(3)N (PONOP-Ar(F); Ar(F) = 2-(CF(3))C(6)H(4)) are described, where the P-donors have ortho-trifluoromethylphenyl substituents. The iridium(iii) 2,2′-biphenyl (biph) derivative [...

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Autores principales: Poole, Ethan W., Bustos, Itxaso, Hood, Thomas M., Smart, Jennifer E., Chaplin, Adrian B.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9872493/
https://www.ncbi.nlm.nih.gov/pubmed/36602231
http://dx.doi.org/10.1039/d2dt03608h
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author Poole, Ethan W.
Bustos, Itxaso
Hood, Thomas M.
Smart, Jennifer E.
Chaplin, Adrian B.
author_facet Poole, Ethan W.
Bustos, Itxaso
Hood, Thomas M.
Smart, Jennifer E.
Chaplin, Adrian B.
author_sort Poole, Ethan W.
collection PubMed
description The synthesis and iridium coordination chemistry of a new pyridine-based phosphinito pincer ligand 2,6-(Ar(F)(2)PO)(2)C(5)H(3)N (PONOP-Ar(F); Ar(F) = 2-(CF(3))C(6)H(4)) 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.
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spelling pubmed-98724932023-02-03 Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand Poole, Ethan W. Bustos, Itxaso Hood, Thomas M. Smart, Jennifer E. Chaplin, Adrian B. Dalton Trans Chemistry The synthesis and iridium coordination chemistry of a new pyridine-based phosphinito pincer ligand 2,6-(Ar(F)(2)PO)(2)C(5)H(3)N (PONOP-Ar(F); Ar(F) = 2-(CF(3))C(6)H(4)) 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. The Royal Society of Chemistry 2022-12-21 /pmc/articles/PMC9872493/ /pubmed/36602231 http://dx.doi.org/10.1039/d2dt03608h Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Poole, Ethan W.
Bustos, Itxaso
Hood, Thomas M.
Smart, Jennifer E.
Chaplin, Adrian B.
Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand
title Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand
title_full Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand
title_fullStr Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand
title_full_unstemmed Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand
title_short Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand
title_sort iridium complexes of an ortho-trifluoromethylphenyl substituted ponop pincer ligand
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9872493/
https://www.ncbi.nlm.nih.gov/pubmed/36602231
http://dx.doi.org/10.1039/d2dt03608h
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