Synthesis and electrochemistry of 2-polymethylmetallocenyl-substituted pyrrolidino[60]fullerenes

Sokolov, V. I.; Abramova, N. V.; Mutseneck, Elena V.; Romanov, Alexander S.; Kudinov, Alexander R.; Zanello, Piero; Barbetti, Jacopo; Peregudova, Svetlana M.

doi:10.1016/j.mencom.2007.06.004

Cited by 6 publications

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“…The Prato reaction is a very convenient synthetic method for the introduction of organometallic fragments into the pyrrolidine ring fused to a fullerene. 18- 20 We used this approach fto synthesize optically active organometal lic derivative 6 starting from planar chiral aldehyde 4 (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

Circular dichroism of optically active organometallic derivatives of fullerenes C60 and C70

et al. 2009

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Section: Resultsmentioning

confidence: 99%

Circular dichroism of optically active organometallic derivatives of fullerenes C60 and C70

et al. 2009

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“…3, 4 We have re cently studied new [60]fullereno[c]pyrrolidine derivatives containing other organometallic substituents, viz., cyman trenyl, (E) 2 cymantrenylvinyl, 5 (tetramethylcyclobuta dienyl)cobalt(cyclopentadienyl), and (pentamethyl)ruthe nocenyl. 6 To extend the range of N methyl 2 cyclopentadie nyltricarbonyl[60]fullereno[c]pyrrolidines, here we used Prato´s reaction between C 60 , N methylglycine (sar cosine), and appropriate aldehydes 1a-d as a route to new derivatives 2a-d containing substituents with stronger electron withdrawing properties than those of ferrocene (Scheme 1). The chiroptical properties of compounds 1d and 2d will be described elsewhere.…”

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Synthesis and properties of N-methyl[60]fullereno[c]pyrrolidines containing cyclopentadienyl(carbonyl)metal fragments

et al. 2008

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In new N methyl[60]fullereno[c]pyrrolidine derivatives, the organometallic substituents in position 2 of the pyrrolidine ring are tricarbonyl(cyclopentadienyl)rhenium, α bicymantrenyl, and β bicymantrenyl (also the optically active (+) enantiomer of the latter). The electrochemi cal and spectroscopic (NMR) properties of the compounds obtained were studied.Fullerenes are known to be strong acceptors capable of taking up to six electrons in solution. Their electrophysical properties can be changed by modifying the C 60 molecule. A possible way of modification is [2+3] cycloaddition of azomethine ylides leading to pyrrolidinofullerenes. This method involves generation of azomethinylides via decar boxylation of immonium salts prepared by condensation of α amino acids with aldehydes. This method is com monly referred to as Prato´s reaction. 1,2In the chemistry of fullerenes, one of the problems associated with their promising use in electronic devices is the synthesis of more electron withdrawing derivatives than C 60 itself. At the same time, it is interesting to obtain derivatives in which the rate of intramolecular electron phototransfer depends on the ratio of the electron dona ting and electron withdrawing properties of their frag ments. A combination of fullerene and organometallic fragments in a molecule allows "fine adjustment" of the degree of intramolecular transfer of the electron density and, consequently, of its electrophysical and optical prop erties. However, only few fullerenopyrrolidines containing organometallic substituents in position 2 of the heterocy cle have been documented. Until recently, such substitu ents included only ferrocenyl fragments. 3, 4 We have re cently studied new [60]fullereno[c]pyrrolidine derivatives containing other organometallic substituents, viz., cyman trenyl, (E) 2 cymantrenylvinyl, 5 (tetramethylcyclobuta dienyl)cobalt(cyclopentadienyl), and (pentamethyl)ruthe nocenyl. 6 To extend the range of N methyl 2 cyclopentadie nyltricarbonyl[60]fullereno[c]pyrrolidines, here we used Prato´s reaction between C 60 , N methylglycine (sar cosine), and appropriate aldehydes 1a-d as a route to new derivatives 2a-d containing substituents with stronger electron withdrawing properties than those of ferrocene (Scheme 1). The chiroptical properties of compounds 1d and 2d will be described elsewhere.

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Synthesis and oxidation of vinyl derivatives of N-methyl[60]fullereno[c]pyrrolidine

2010

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Novel organometallic derivatives of N methyl[60]fullereno [c]pyrrolidine bearing the vinyl fragment at the position 2 of the pyrrolidine ring were synthesized. Their oxidation with 3 chloroperoxybenzoic acid to give N oxides and epoxides was studied in detail.It is known from the numerous publications on ful lerenes that [60]fullerene can be modified by 1,3 dipolar cycloaddition of azomethine ylides (the Prato reaction), which led to various fullerenopyrrolidines. 1,2Oxidation of fullerenopyrrolidine derivatives at the nitrogen atom to give fullerenopyrrolidine N oxides 3 could be regarded as one of the promising methods for further functionalization of this class of compounds. Studying this reaction is of interest because the N oxides are used to protect an amino group during subsequent transforma tions of the molecule. A number of N oxides bearing or ganic substituents at the position 2 of the pyrrolidine ring were synthesized. 3 Organometallic derivatives of fullereno pyrrolidines are of interest due to the effect of the metal atom on the oxidation. Besides, fullerene derivatives bear ing double bond are promising because in their case both the oxidation of the nitrogen atom and the formation of an epoxide could occur. In the present work with the aim at studying this process, from N methylglycine 1 and alde hydes 2a-e, we synthesized the corresponding fullereno pyrrolidines 3a-e (Scheme 1).Oxidation of organometallic derivatives of fullereno pyrrolidines 3a,b with equimolar amount of 3 chloroper oxybenzoic acid (mCPBA) resulted in compounds 4a,b in the yields of 34 and 44%, respectively. In the 1 H NMR spectra of the synthesized compounds, all signals shifted downfield by 0.6-1.0 ppm with respect to the starting fullerenopyrrolidines. This fact is consistent with the pub lished data 3 suggesting that the oxidation occurred at the nitrogen atom of the pyrrolidine fragment. The downfield shift of the signal for the NMe group is the most charac teristic. Thus, these shifts are 0.5 and 0.8 ppm for com pounds 4a and 4b, respectively. No paramagnetism was observed in the NMR spectra of the compounds synthe sized indicating that the metal atom in the organometallic fragment of the molecule does not oxidized, i.e., the pres ence of the metal atom does not affect the oxidation of the fullerenopyrrolidine with mCPBA. Scheme 1

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Synthesis and electrochemistry of 2-polymethylmetallocenyl-substituted pyrrolidino[60]fullerenes

Cited by 6 publications

References 10 publications

Circular dichroism of optically active organometallic derivatives of fullerenes C60 and C70

Circular dichroism of optically active organometallic derivatives of fullerenes C60 and C70

Synthesis and properties of N-methyl[60]fullereno[c]pyrrolidines containing cyclopentadienyl(carbonyl)metal fragments

Synthesis and oxidation of vinyl derivatives of N-methyl[60]fullereno[c]pyrrolidine

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