Topochemical solid-state reactions and problems of selective synthesis of fullerene derivatives

Borshchevskii, A. Ya.; Sidorov, Lev N.; Chilingarov, N. S.; Aleshina, V. E.

doi:10.1007/s11172-005-0214-7

Cited by 4 publications

(3 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[40] Another interesting example is the application of the BEP principle to a sort of "inverse problem", that is, the estimation of enthalpies and activation energies as a function of the degree of fluorination on the basis of time-resolved analysis of synthetic products. [25,41,42] It has been confirmed experimentally that changes in the above enthalpies due to different choices of fluorinating agents can, indeed, result in drastic changes in the major products that agree with predictions based on the enthalpy-activation-energy linear correlation. In particular, it has been shown how to switch the C 60 /solid fluorinating agent system between producing C 60 F 18 and C 60 F 36 .…”

Section: Mechanistic Considerationssupporting

confidence: 68%

“…It can be expected that the listed isomers overlap considerably with those 13 isomers of C 60 (CF 3 ) 6 detected previously. [6] It would be of particular interest to trace subsequent trifluoromethylation up to C 60 (CF 3 ) 10 and C 60 (CF 3 ) 12 and to rationalize the formation of such isomers as 1,6,12,15,18,23,25,41,45,57-C 60 (CF 3 ) 10 with two mpppm loops of CF 3 groups, with isomers 6-2, 6-3, 6-4, 6-13, and 6-14 of C 60 (CF 3 ) 6 acting as precursors, or (S 6 )-C 60 (CF 3 ) 12 , with isomer 6-6 of C 60 (CF 3 ) 6 as a possible precursor. The determination of sufficiently probable pathways that yield these compounds would be an important test of validity of our model.…”

Section: Mechanistic Considerationsmentioning

confidence: 99%

“…Such a representative set of X-ray data, accompanied by extensive DFT calculations of the relative stability of C 60 (CF 3 ) n isomers (n = 2-6), have allowed a mechanistic model to be proposed for the consecutive addition of CF 3 groups to [60]fullerene, a systematic analysis of the addition patterns governing the trifluoromethylation of C 60 to form C 60 (CF 3 ) n up to n = 6, and a comparison of our approach with those developed for fluorofullerenes. [24,25] …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis, Structure, and Theoretical Study of Lower Trifluoromethyl Derivatives of [60]Fullerene

et al. 2007

View full text Add to dashboard Cite

A number of C60(CF3)n compounds with n = 2–10 have been synthesized by the reaction of C60 with silver trifluoroacetate and successfully isolated by means of HPLC. This resulted in the first crystal structure determination of six lower trifluoromethyl derivatives with n = 2 (single isomer), 4 (two isomers), and 6 (three isomers). A kinetic model of sequential trifluoromethylation based on the Bell–Evans–Polanyi principle has been used to explain the experimentally observed isomeric distribution in the mixtures of C60(CF3)n compounds up ton = 6. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

show abstract

Section: Mechanistic Considerationssupporting

confidence: 68%

Section: Mechanistic Considerationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, Structure, and Theoretical Study of Lower Trifluoromethyl Derivatives of [60]Fullerene

et al. 2007

View full text Add to dashboard Cite

show abstract

Topochemical Solid‐State Reactions and Problems of Selective Synthesis of Fullerene Derivatives

et al. 2005

View full text Add to dashboard Cite

show abstract

Trifluoromethylation of Fullerenes: Kinetic and Thermodynamic Control

et al. 2013

View full text Add to dashboard Cite

We present a survey and theoretical interpretation of the experimental results on trifluoromethylation of fullerenes. A thermodynamic model has been developed to describe the C60/70(CF3)n condensed phase mixtures capable of free exchange of addends and, consequently, of isomerization and changing the degrees of addition. It was found that the purely thermodynamic model affords at least satisfactory prediction of composition of products even for apparently nonequilibrium syntheses. Special cases can be identified by means of detailed kinetic modeling based on the BEP approach, which includes stepwise energetic analysis of the possible trifluoromethylation sequences. This analysis reveals two types of reactions with remarkable difference in rates: direct trifluoromethylation and rearrangements of the CF3 groups. Whenever a particular group of compounds is interrelated through direct addition/abstraction of CF3 groups, it is more or less safe to assume that the said group is in equilibrium describable by the thermodynamic model. In the same time, the slower migration of addends is controlled kinetically, and interference of the sublimation processes frequently prevents its equilibration. Among the most illustrative examples of hindered formation via rearrangements in absence of sufficiently favorable direct trifluoromethylation pathways are certain isomers of the C3v-C60(CF3)18, C70(CF3)18, and C70(CF3)20 compounds.

show abstract

Topochemical solid-state reactions and problems of selective synthesis of fullerene derivatives

Cited by 4 publications

References 30 publications

Synthesis, Structure, and Theoretical Study of Lower Trifluoromethyl Derivatives of [60]Fullerene

Synthesis, Structure, and Theoretical Study of Lower Trifluoromethyl Derivatives of [60]Fullerene

Topochemical Solid‐State Reactions and Problems of Selective Synthesis of Fullerene Derivatives

Trifluoromethylation of Fullerenes: Kinetic and Thermodynamic Control

Contact Info

Product

Resources

About