Publication detail

Polymethylated [Fe(eta(6)-arene)(2)](2+) dications: methyl-group rearrangements and application of the EINS mechanism.

Year: 2011

Type of publication: článek v odborném periodiku

Name of source: Dalton Transactions

Publisher name: Royal Society of Chemistry

Place: Cambridge

Page from-to: 5916-5920

Titles:

Language	Name	Abstract	Keywords
cze	Polymethylované [Fe(eta(6)-aren)(2)](2+) dicationty: vliv methyl skupiny a aplikace v EINS mechanizmu	Reakce mezi metylovanými areney ArMe(n) [kde ArMe(n) = C(6)Me(n)H((6-n)), a n = 1-6] a FeCl(2) v heptanu za 90 stupních v přítomnosti bezvodého AlCl(3) poskytuje, pro areney s n = 1-5, rozsáhlé izomerace a disproporcionace metylových skupin na arenových kruzích za vzniku směsí [Fe(ArMe(n))(2)](2+). GC-MS studie AlCl(3)/mesitylenu a AlCl(3)/durenu reakcí za nepřítomnosti FeCl(2) (90 stupňů, 2 h) dokazují kvantitativní ustanovení a EINS mechanismus (elektrofilem indukovaná nukleofilní substituce) je aplikována. Naopak ArMe(n)/FeCl(2)/AlCl(3) reakce v heptanu po 24 - 36 h za rt neposkytuje žádné přerovnání, způsobuje však syntézu kompletní série [Fe(ArMen)](2+) ionů ve výtěžkách 48 - 71%. Čisté sloučeniny byly charakterizovány pomocí (1)H NMR spektroskopiemi a elektrospray- ionizací hmotnostní spektrometrií (ESI MS), a struktury [Fe(m-xylene)(2)][PF(6)](2) a [Fe(durene)(2)][PF(6)](2) byly určeny rentgenovou difrakcí.	Komplexy
eng	Polymethylated [Fe(eta(6)-arene)(2)](2+) dications: methyl-group rearrangements and application of the EINS mechanism.	Reactions between the methylated arenes ArMe(n) [where ArMe(n) = C(6)Me(n)H((6-n)), and n = 1-6] and FeCl(2) in heptane at 90 degrees C in the presence of anhydrous AlCl(3) give, for the arenes with n = 1-5, extensive isomerisations and disproportionations involving the methyl groups on the arene rings, and the formation of mixtures of [Fe(ArMe(n))(2)](2+) dications that defy separation into pure species. GC-MS studies of AlCl(3)/mesitylene and AlCl(3)/durene reactions in the absence of FeCl(2) (90 degrees C, 2 h) allow quantitative assessments of the rearrangements, and the EINS mechanism (electrophile-induced nucleophilic substitution) is applied to rationalise the phenomena. By contrast, ArMe(n)/FeCl(2)/AlCl(3) reactions in heptane for 24-36 h at room-temperature proceed with no rearrangements, allowing the synthesis of the complete series of pure [Fe(ArMen)](2+) cations in yields of 48-71%. The pure compounds are characterised by (1)H NMR spectroscopy and electrospray-ionization mass-spectrometry (ESI-MS), and the structures of [Fe(m-xylene)(2)][PF(6)](2) and [Fe(durene)(2)][PF(6)](2) are established by single-crystal X-ray diffraction analyses.	Complexes

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