Synthesis and fluxional behaviour of new “heavy fluorous” cyclopentadienes

Šťastná, Lucie Červenková; Čermák, Jan; Cuřínová, Petra; Sýkora, Ján

doi:10.1016/j.jorganchem.2009.11.021

Cited by 8 publications

(1 citation statement)

References 26 publications

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“…1, p. 247], brought so far several novel types of cyclopentadienes and cyclopentadienyl complexes made fluorophilic by the attachment of polyfluorinated chains – fluorous ponytails. These include cyclopentadienes with one [9], two [10,11,12] or more [13,14] (perfluoroalkyl)ethyl chains, cyclopentadienes with silicon atoms directly bonded to the ring to separate electronic effects of the fluorous ponytail [15,16,17,18] and cyclopentadienes monosubstituted with perfluoroalkyl chains [9], which are difficult to handle or use for metal complexation. The last of the so far known types of fluorous cyclopentadienes is represented by the (perfluoroalkyl)tetramethylcyclopentadienes prepared in our group [16,19,20,21].…”

Section: Introductionmentioning

confidence: 99%

Dehydration of (Perfluoroalkyl)tetramethylcyclopentenols

et al. 2011

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(Perfluoroalkyl) tetramethylcyclopentenols (alkyl = n-butyl, n-hexyl, n-octyl) were dehydrated to a complex mixture of endo, endo-(perfluoroalkyl) tetramethyl-cyclopentadienes and their endo-, exo-isomers. It was found in preliminary screening experiments that the best reagent for this transformation, giving an 89% yield of isomeric product mixture, was P2O5 in benzene at 80-90 °C. Products were characterized on the basis of their mass spectra and retention time information, and some peaks in the mass spectra were identified from their molecular fragments. Structures were assigned to the three most abundant products of (perfluorohexyl)tetramethylcyclopentenol dehydration. Formal dehydration kinetics showed a second order reaction in benzene but zeroth order with induction period in chlorobenzene, suggesting mass transfer limitations in the more polar chlorobenzene. Some of the products were formed by consecutive isomerization of the others, as shown by the kinetic analysis.

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Section: Introductionmentioning

confidence: 99%

Dehydration of (Perfluoroalkyl)tetramethylcyclopentenols

et al. 2011

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Fluorous Organometallic Chemistry

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Simayi

Stuart

2015

Topics in Organometallic Chemistry

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Carbosilane Metallodendrimers with Cyclopentadienyldichlorotitanium(IV) End Groups

Krupková

Čermák

2011

J Inorg Organomet Polym

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Dendritic polyols of the second and third generation 2G-OH 8 (1), 2G-OH 16 (2), and 3G-OH 16 (3) were prepared by hydroboration/oxidation of allyl-terminated carbosilane dendrimers and used as supports for the immobilization of cyclopentadienyltrichlorotitanium(IV) complexes via alcoholysis. The reaction of 1-3 with CpTiCl 3 gave metallodendrimers 2G-(OTiCpCl 2 ) 8 (4a), 2G-(OTiCpCl 2 ) 16 (5a), and 3G-(OTiCpCl 2 ) 16 (6a), respectively, whereas the reaction of 1 and 3 with CpSi F TiCl 3 (CpSi F = C 5 H 4 SiMe 2 CH 2 CH 2 C 8 F 17 ) yielded peripherally fluorinated metallodendrimers 2G-(OTiCpSi F Cl 2 ) 8 (4b) and 3G-(OTiCpSi F Cl 2 ) 16 (6b). All metallodendrimers were characterized by multinuclear NMR spectroscopy. The suggested structures were supported by comparison with model 1-propoxycomplexes 10a,b. To identify side products of the alcoholysis reaction, hydrolytic behavior of the starting trichloro complexes was studied both in solid state and in solution. The main products of hydrolysis in solution were identified as l-oxocomplexes 8a,b whereas hydrolysis in solid state yielded mainly hydroxycomplexes 7a,b.

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Synthesis and fluxional behaviour of new “heavy fluorous” cyclopentadienes

Cited by 8 publications

References 26 publications

Dehydration of (Perfluoroalkyl)tetramethylcyclopentenols

Dehydration of (Perfluoroalkyl)tetramethylcyclopentenols

Fluorous Organometallic Chemistry

Carbosilane Metallodendrimers with Cyclopentadienyldichlorotitanium(IV) End Groups

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