Multi-Ferrocenyl Aryl Ethers - Applying Nucleophilic Aromatic Substitution Reactions to Aryl Fluorides

Marcus Korb, Heinrich Lang

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The reaction of ferrocenol [FcOH; Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)] with aryl fluorides ArH6-nFn (n = 3-6) within a nucleophilic aromatic substitution reaction (SNAr) gave ferrocenyloxy-substituted fluorobenzenes of general type C6H0-3F1-5(OFc)(1-5). For 1,3,5-C6H3F3, 1,2,4,5-C6H2F4, and C6H6-nFn (n = 5,6), one, two, and three F atoms, respectively, could be replaced by FcO units. The reaction of 1,4-(OFc)(2)-C6F4 with additional amounts of FcOH afforded the tetra- and penta-substituted arenes 3,6-F-2-C-6(OFc)(4) and C6F(OFc)(5). Electrochemical investigations of both compounds showed four or five Fc/Fc(+) related reversible redox processes that were attributed to electrostatic interactions. The addition of C6F6 as the electrophile after the anionic phospho-Fries rearrangement of a ferrocenyl phosphate (1,3-OC migration) to the 1,2-substituted ortho-phosphonato ferrocenol, resulted in the formation of the respective ortho-functionalized ether. The constitution of all compounds was verified by using F-19 NMR spectroscopy. Steric hindrance of the ortho-substituent resulted in a doubling of the signal sets for the C6F5 moiety in the C-13{H-1} and F-19 NMR spectra. The identity and substitution pattern of five compounds could also be determined by using single-crystal X-ray diffraction analysis, revealing the 1,4-constitution of double functionalized derivatives, intermolecular non-classical C-H center dot center dot center dot F interactions and pi interactions.

Original languageEnglish
Pages (from-to)276-287
Number of pages12
JournalEuropean Journal of Inorganic Chemistry
Issue number2
DOIs
Publication statusPublished - Jan 2017
Externally publishedYes

Cite this

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title = "Multi-Ferrocenyl Aryl Ethers - Applying Nucleophilic Aromatic Substitution Reactions to Aryl Fluorides",
abstract = "The reaction of ferrocenol [FcOH; Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)] with aryl fluorides ArH6-nFn (n = 3-6) within a nucleophilic aromatic substitution reaction (SNAr) gave ferrocenyloxy-substituted fluorobenzenes of general type C6H0-3F1-5(OFc)(1-5). For 1,3,5-C6H3F3, 1,2,4,5-C6H2F4, and C6H6-nFn (n = 5,6), one, two, and three F atoms, respectively, could be replaced by FcO units. The reaction of 1,4-(OFc)(2)-C6F4 with additional amounts of FcOH afforded the tetra- and penta-substituted arenes 3,6-F-2-C-6(OFc)(4) and C6F(OFc)(5). Electrochemical investigations of both compounds showed four or five Fc/Fc(+) related reversible redox processes that were attributed to electrostatic interactions. The addition of C6F6 as the electrophile after the anionic phospho-Fries rearrangement of a ferrocenyl phosphate (1,3-OC migration) to the 1,2-substituted ortho-phosphonato ferrocenol, resulted in the formation of the respective ortho-functionalized ether. The constitution of all compounds was verified by using F-19 NMR spectroscopy. Steric hindrance of the ortho-substituent resulted in a doubling of the signal sets for the C6F5 moiety in the C-13{H-1} and F-19 NMR spectra. The identity and substitution pattern of five compounds could also be determined by using single-crystal X-ray diffraction analysis, revealing the 1,4-constitution of double functionalized derivatives, intermolecular non-classical C-H center dot center dot center dot F interactions and pi interactions.",
keywords = "Aromatic substitution, Ferrocene, Redox chemistry, Fluorine, Fries rearrangement, SOLID-STATE STRUCTURE, ONE-POT APPROACH, POLYFLUORO-COMPOUNDS, REPLACEMENT REACTIONS, FRIES REARRANGEMENTS, CRYSTAL-STRUCTURE, AMMONIUM IODIDE, ELECTROCHEMISTRY, REACTIVITY, CYANATION",
author = "Marcus Korb and Heinrich Lang",
year = "2017",
month = "1",
doi = "10.1002/ejic.201600850",
language = "English",
pages = "276--287",
journal = "European Journal of Inorganic Chemistry",
issn = "1099-0682",
publisher = "Wiley-VCH Verlag GmbH & Co. KGaA",
number = "2",

}

Multi-Ferrocenyl Aryl Ethers - Applying Nucleophilic Aromatic Substitution Reactions to Aryl Fluorides. / Korb, Marcus; Lang, Heinrich.

In: European Journal of Inorganic Chemistry, No. 2, 01.2017, p. 276-287.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Multi-Ferrocenyl Aryl Ethers - Applying Nucleophilic Aromatic Substitution Reactions to Aryl Fluorides

AU - Korb, Marcus

AU - Lang, Heinrich

PY - 2017/1

Y1 - 2017/1

N2 - The reaction of ferrocenol [FcOH; Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)] with aryl fluorides ArH6-nFn (n = 3-6) within a nucleophilic aromatic substitution reaction (SNAr) gave ferrocenyloxy-substituted fluorobenzenes of general type C6H0-3F1-5(OFc)(1-5). For 1,3,5-C6H3F3, 1,2,4,5-C6H2F4, and C6H6-nFn (n = 5,6), one, two, and three F atoms, respectively, could be replaced by FcO units. The reaction of 1,4-(OFc)(2)-C6F4 with additional amounts of FcOH afforded the tetra- and penta-substituted arenes 3,6-F-2-C-6(OFc)(4) and C6F(OFc)(5). Electrochemical investigations of both compounds showed four or five Fc/Fc(+) related reversible redox processes that were attributed to electrostatic interactions. The addition of C6F6 as the electrophile after the anionic phospho-Fries rearrangement of a ferrocenyl phosphate (1,3-OC migration) to the 1,2-substituted ortho-phosphonato ferrocenol, resulted in the formation of the respective ortho-functionalized ether. The constitution of all compounds was verified by using F-19 NMR spectroscopy. Steric hindrance of the ortho-substituent resulted in a doubling of the signal sets for the C6F5 moiety in the C-13{H-1} and F-19 NMR spectra. The identity and substitution pattern of five compounds could also be determined by using single-crystal X-ray diffraction analysis, revealing the 1,4-constitution of double functionalized derivatives, intermolecular non-classical C-H center dot center dot center dot F interactions and pi interactions.

AB - The reaction of ferrocenol [FcOH; Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)] with aryl fluorides ArH6-nFn (n = 3-6) within a nucleophilic aromatic substitution reaction (SNAr) gave ferrocenyloxy-substituted fluorobenzenes of general type C6H0-3F1-5(OFc)(1-5). For 1,3,5-C6H3F3, 1,2,4,5-C6H2F4, and C6H6-nFn (n = 5,6), one, two, and three F atoms, respectively, could be replaced by FcO units. The reaction of 1,4-(OFc)(2)-C6F4 with additional amounts of FcOH afforded the tetra- and penta-substituted arenes 3,6-F-2-C-6(OFc)(4) and C6F(OFc)(5). Electrochemical investigations of both compounds showed four or five Fc/Fc(+) related reversible redox processes that were attributed to electrostatic interactions. The addition of C6F6 as the electrophile after the anionic phospho-Fries rearrangement of a ferrocenyl phosphate (1,3-OC migration) to the 1,2-substituted ortho-phosphonato ferrocenol, resulted in the formation of the respective ortho-functionalized ether. The constitution of all compounds was verified by using F-19 NMR spectroscopy. Steric hindrance of the ortho-substituent resulted in a doubling of the signal sets for the C6F5 moiety in the C-13{H-1} and F-19 NMR spectra. The identity and substitution pattern of five compounds could also be determined by using single-crystal X-ray diffraction analysis, revealing the 1,4-constitution of double functionalized derivatives, intermolecular non-classical C-H center dot center dot center dot F interactions and pi interactions.

KW - Aromatic substitution

KW - Ferrocene

KW - Redox chemistry

KW - Fluorine

KW - Fries rearrangement

KW - SOLID-STATE STRUCTURE

KW - ONE-POT APPROACH

KW - POLYFLUORO-COMPOUNDS

KW - REPLACEMENT REACTIONS

KW - FRIES REARRANGEMENTS

KW - CRYSTAL-STRUCTURE

KW - AMMONIUM IODIDE

KW - ELECTROCHEMISTRY

KW - REACTIVITY

KW - CYANATION

U2 - 10.1002/ejic.201600850

DO - 10.1002/ejic.201600850

M3 - Article

SP - 276

EP - 287

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1099-0682

IS - 2

ER -