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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 [...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2022
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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. |
format | Online Article Text |
id | pubmed-9872493 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
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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