Electronic properties of the ferrocenyl as a substituent

Nesmeyanov, A. N.; Perovalova, E.G.; Губин, С. П.; Grandberg, K. I.; Kozlovsky, A.G.

doi:10.1016/s0040-4039(00)75663-2

Cited by 38 publications

(17 citation statements)

References 7 publications

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“…8). In accordance with the known inductive electron donating effect of the ferrocene moiety, directly connected to the conjugated dipyrrin fragment, 36 the sole reduction process in 1 is observed as a quasi reversible wave at a slightly higher potential than in the meso-tolyl analogue 6 (DE ≈ 50 mV).…”

Section: Meso-ferrocenyl Calixphyrinssupporting

confidence: 78%

Calix[4]phyrin based redox architectures: towards new molecular tools for electrochemical sensing

et al. 2005

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New redox active molecular macrocyclic architectures characterized by a direct connection between dipyrrin, tripyrrin and ferrocenyl fragments have been synthesized and characterized. Contrarily to fully conjugated porphyrins, in which four pyrrole moieties contribute to the overall aromatic pi-electronic system and behave as a unique electroactive species, calixphyrins can be regarded as an assembly of independent redox active pyrrole and conjugated oligopyrrole fragments linked through sp(3) hybridized meso carbon atoms. The disruption of the conjugation pathway not only multiplies the number of redox centres throughout the molecule but also leads to a large variety of molecular architectures with specific physico-chemical properties. These novel ferrocene containing hybrid macrocycles exhibit especially attractive electronic and structural features suited for use as molecular sensing tools. An efficient voltammetric sensing of exogenic electron rich anionic species could especially be performed using a metallo-calix[4]phyrin-(1.1.1.1) through the displacement of the labile axial binding site, the perturbation of the Fc(0/+) redox couple being directly related to complexed species features.

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Section: Meso-ferrocenyl Calixphyrinssupporting

confidence: 78%

Calix[4]phyrin based redox architectures: towards new molecular tools for electrochemical sensing

et al. 2005

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“…This was also observed for the Fc-arylamine derivative of lawsone. 18 Good correlation of the E 1/2 (1) potentials with the s p and s p -Hammett constants 42 was obtained (Figures 6 and 7, respectively) except for the Fc group ( Figure 7) for which the low s p -value (-0.03) 43 has been correlated to low resonance contribution. The linear correlation coefficients for both plots suggest that all naphthoquinones of this series are reduced by the same mechanism.…”

Section: Cyclic Voltammetrymentioning

confidence: 83%

Novel 2-(R-phenyl)amino-3-(2-methylpropenyl)-[1,4]-naphthoquinones: synthesis, characterization, electrochemical behavior and antitumor activity

Casellato¹,

Neves²,

Carneiro³

et al. 2010

J. Braz. Chem. Soc.

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Novas 2-(R-fenil)amino-3-(2-metilpropenil)-[1,4]-naftoquinonas (R = H, 4-OMe, 4-Ferrocenil, 4-Me, 3-Me, 4-I, 3-I, 4-CN, 3-CN, 4-NO 2 e 3-NO 2 ) derivadas do nor-lapachol [2-hidroxi-3-(2-metilpropenil)-1,4-naftoquinona] foram obtidas em bons rendimentos. A estrutura dos compostos foi proposta com base em estudos de difração de raios-X (R = OMe, 2b), dados de RMN de 1 H e 13 C e cálculos teóricos utilizando o funcional B3LYP e a base 6-311+G(2d,p). Os potenciais de meia-onda das aminonaftoquinonas e o deslocamento químico do hidrogênio da cadeia 3-propenil dos compostos 2a-k mostraram boa correlação com as constantes de Hammett dos substituintes presentes no anel fenileno. A avaliação da citotoxicidade evidenciou atividade antitumoral promissora para o substrato metóxi-nor-lapachol 1 e o derivado 4-ferrocenil 2c.Novel 2-(R-phenyl)amino-3-(2-methyl-propenyl)-[1,4]-naphthoquinones (R = H, 4-OMe, 4-Ferrocenyl, 4-Me, 3-Me, 4-I, 3-I, 4-CN, 3-CN, 4-NO 2 and 3-NO 2 ) derived from nor-lapachol [2-hydroxy-3-(2-methylpropenyl)-1,4-naphthoquinone] were obtained in good yields. Their structures were proposed on the basis of a single crystal X-ray diffraction study (R = OMe, 2b), 1 H and 13 C NMR studies and calculations using the B3LYP functional and the 6-311+G(2d,p) basis set. The half-wave potentials of the aminonaphthoquinones and 1 H NMR chemical shifts of the 3-propenyl hydrogen in 2a-k show good correlation with the substituent Hammett constants on the phenylamino ring. The antitumor assays showed promising activity for substrate methoxynor-lapachol 1 and the 4-ferrocenyl derivative 2c.Keywords: Nor-lapachol, arylamine, aminonaphthoquinone, electrochemistry, B3LYP, antitumor activity IntroductionNaphthoquinones are widely distributed in nature and some of these molecules have an important role in the biochemistry of microbial energy production, by means of photosynthesis and respiratory chain.1 Compounds containing the quinone group are known for exhibiting antitumor, 2 trypanocide, 3 moluscicide, 4 fungicide 5 and antimalarial 6 activities. The presence of an amino group in quinones has led to interesting biologically active compounds. 7-12Biological activity of quinones is often related to their electrochemical behavior. 13 The ability to accept one or two electrons to form the corresponding radical anion (Q •-) or dianion (Q 2-) species is believed to induce formation of reactive oxygen species, responsible for the oxidative stress in cells.14 The electron-accepting capacity of naphthoquinones may be tuned by carbonyl position changes (1,2-x 1,4-naphthoquinones) 15 or different substituents or functions attached to the naphthoquinone moiety, and the use of electrochemical methods to study Braz. Chem. Soc. 170 this type of molecules has proven to be useful. 16,17 We reported recently 18 the synthesis of a series of 2-arylamino-1,4-naphthoquinones from 2-methoxy-1,4-naphthoquinone and arylamines in the presence of MgCl 2• 6H 2 O and p-toluenesulfonic acid as catalysts. The reactions of both electron-donor and...

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“…This may suggest that the sterics play a significant role in the formation of the products as the yields decrease and the reaction times increase when the steric hindrance of the substituents of the starting diketone reagents increases. The electron donating ability of both 4-methoxyphenyl and ferrocenyl groups are known to be similar [22]. On the other hand, compound 1 was previously prepared in 90% yield by reaction of 1-ferrocenyl ethanol with 2,4-pentanedione, in water at 80 °C for 24 h [10].…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

Synthesis, characterization and X-ray crystal structures of chiral ferrocene-containing β-diketones

Ahumada

Roisnel

Sinbandhit

et al. 2013

Journal of Organometallic Chemistry

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CCDC 922490, 922491, and 922492 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.International audienceThree new chiral ferrocene-containing β-diketones have been synthesized by reacting 1-ferrocenyl ethanol with the corresponding 1,3-diketone reagent MeCOCH2COR (R = Me, 4-C6H4OMe, Fc; Fc = (η5-C5H5)Fe(η5-C5H4)), using cerium(IV) ammonium nitrate (CAN) mediated C-C bond formation. These compounds identified as 3-(1-ferrocenylethyl)-pentane-2,4-dione (1), 1-(4-methoxyphenyl)-2-(1-ferrocenylethyl)-butane-1,3-dione (2), and 1-ferrocenyl-2-(1-ferrocenylethyl)-butane-1,3-dione (3), have been isolated as air and thermally stable microcrystalline solids in 79, 63 and 44% yields, respectively. Compounds 2 and 3 were formed in 63:37 and 88:12 diastereomeric ratios, respectively. They have been fully characterized by elemental analyses, FT-IR spectra, mass spectrometry, and their complete assignments have been conducted using 2D NMR experiments. In addition, their molecular identity and geometry have been confirmed by single-crystal X-ray diffraction, and both solution and solid state measurements have shown that the three complexes exist solely as their diketo tautomers

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Electronic properties of the ferrocenyl as a substituent

Cited by 38 publications

References 7 publications

Calix[4]phyrin based redox architectures: towards new molecular tools for electrochemical sensing

Calix[4]phyrin based redox architectures: towards new molecular tools for electrochemical sensing

Novel 2-(R-phenyl)amino-3-(2-methylpropenyl)-[1,4]-naphthoquinones: synthesis, characterization, electrochemical behavior and antitumor activity

Synthesis, characterization and X-ray crystal structures of chiral ferrocene-containing β-diketones

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