A T-shaped Ni[κ(2)-(CF(2))(4)–] NHC complex: unusual C(sp(3))–F and M–C(F) bond functionalization reactions

A T-shaped octafluoronickelacyclopentane–NHC complex is prepared and characterized. While the solid-state structure includes a weak isopropyl-CH(3) agostic interaction, the reactivity of this complex with Lewis- and Brønsted acids is clearly enhanced by its low coordination number. Reaction with Me(...

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Autores principales: Andrella, Nicholas O., Sicard, Alexandre J., Gorelsky, Serge I., Korobkov, Ilia, Baker, R. Tom
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2015
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6054117/
https://www.ncbi.nlm.nih.gov/pubmed/30090259
http://dx.doi.org/10.1039/c5sc01886b
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author Andrella, Nicholas O.
Sicard, Alexandre J.
Gorelsky, Serge I.
Korobkov, Ilia
Baker, R. Tom
author_facet Andrella, Nicholas O.
Sicard, Alexandre J.
Gorelsky, Serge I.
Korobkov, Ilia
Baker, R. Tom
author_sort Andrella, Nicholas O.
collection PubMed
description A T-shaped octafluoronickelacyclopentane–NHC complex is prepared and characterized. While the solid-state structure includes a weak isopropyl-CH(3) agostic interaction, the reactivity of this complex with Lewis- and Brønsted acids is clearly enhanced by its low coordination number. Reaction with Me(3)SiOTf, for example, yielded a rare metal–heptafluorocyclobutyl complex whereas carboxylic acids gave substitution at the α-carbon and/or Ni–C(F) bond protonolysis to afford thermally robust 4H-octafluorobutyl Ni complexes.
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spelling pubmed-60541172018-08-08 A T-shaped Ni[κ(2)-(CF(2))(4)–] NHC complex: unusual C(sp(3))–F and M–C(F) bond functionalization reactions Andrella, Nicholas O. Sicard, Alexandre J. Gorelsky, Serge I. Korobkov, Ilia Baker, R. Tom Chem Sci Chemistry A T-shaped octafluoronickelacyclopentane–NHC complex is prepared and characterized. While the solid-state structure includes a weak isopropyl-CH(3) agostic interaction, the reactivity of this complex with Lewis- and Brønsted acids is clearly enhanced by its low coordination number. Reaction with Me(3)SiOTf, for example, yielded a rare metal–heptafluorocyclobutyl complex whereas carboxylic acids gave substitution at the α-carbon and/or Ni–C(F) bond protonolysis to afford thermally robust 4H-octafluorobutyl Ni complexes. Royal Society of Chemistry 2015-11-01 2015-08-06 /pmc/articles/PMC6054117/ /pubmed/30090259 http://dx.doi.org/10.1039/c5sc01886b Text en This journal is © The Royal Society of Chemistry 2015 https://creativecommons.org/licenses/by-nc/3.0/This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)
spellingShingle Chemistry
Andrella, Nicholas O.
Sicard, Alexandre J.
Gorelsky, Serge I.
Korobkov, Ilia
Baker, R. Tom
A T-shaped Ni[κ(2)-(CF(2))(4)–] NHC complex: unusual C(sp(3))–F and M–C(F) bond functionalization reactions
title A T-shaped Ni[κ(2)-(CF(2))(4)–] NHC complex: unusual C(sp(3))–F and M–C(F) bond functionalization reactions
title_full A T-shaped Ni[κ(2)-(CF(2))(4)–] NHC complex: unusual C(sp(3))–F and M–C(F) bond functionalization reactions
title_fullStr A T-shaped Ni[κ(2)-(CF(2))(4)–] NHC complex: unusual C(sp(3))–F and M–C(F) bond functionalization reactions
title_full_unstemmed A T-shaped Ni[κ(2)-(CF(2))(4)–] NHC complex: unusual C(sp(3))–F and M–C(F) bond functionalization reactions
title_short A T-shaped Ni[κ(2)-(CF(2))(4)–] NHC complex: unusual C(sp(3))–F and M–C(F) bond functionalization reactions
title_sort t-shaped ni[κ(2)-(cf(2))(4)–] nhc complex: unusual c(sp(3))–f and m–c(f) bond functionalization reactions
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6054117/
https://www.ncbi.nlm.nih.gov/pubmed/30090259
http://dx.doi.org/10.1039/c5sc01886b
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