The selective reduction of CO2 is of high interest toward future applications as a C1-building block. Therefore, metal complexes that allow for the formation of specific CO2 reduction products under distinct reaction conditions are necessary. A detailed understanding of the CO2 reduction pathways on a molecular level is, however, required to help in designing catalytic platforms for efficient CO2 conversion with specific product formation. Reported herein is a unique example of a solvent-controlled reduction of CO2 using a Triphos-based iron hydride complex. In THF, CO2 reduction selectively leads to CO formation, whereas experiments in acetonitrile exclusively afford formate, HCOO–. In order to explain the experimental findings, theoretical calculations of the reaction pathways were performed and further demonstrate the importance of the applied solvent for a selective reduction of CO2.

We report the synthesis of mono- and 1,1'-difluoro-substituted metallocenes (ferrocene, ruthenocene) and of asymmetrical 1,1'-disubstituted ferrocenes with one substituent being fluorine. Lithiation of metallocenes and subsequent addition of the fluorinating agent NFSI gave the fluorinated metallocenes after optimization of the experimental conditions. All new compounds were comprehensively characterized and the cyclic voltammograms of fluoro-and 1,1'-difluoroferrocene were recorded and compared to other mono- and dihalogenated ferrocenes. Half-wave potentials of +106 mV and +220 mV vs. FcH(0/+) were obtained for monofluorinated species and difluorinated ferrocene, respectively. Both values are remarkably low compared to the other halogenated ferrocenes (Cl, Br, and I). Finally, 1-bromo-1'-fluoroferrocene turns out to be an ideal starting material for further fluoro-substituted ferrocene derivatives. (C) 2015 Published by Elsevier B.V.

We report the synthesis of metallocene compounds Cp2M with two different electron-withdrawing substituents on both cyclopentadienyl rings (hexafluoroacetone (HFA) and chlorobenzoyl (1-5); HFA and COOH (6 and 7), M=Fe or Ru). The COOH-containing derivatives were used to synthesize peptide bioconjugates with enkephalin (8 and 9) and neurotensin (10 and 11) as well as fluorescein-labeled neurotensin (12). All the molecules were fully characterized, including X-ray structures for 6 and 7. The physicochemical properties (lipophilicity and electrochemistry) and cytotoxicity on MCF-7, HT-29, and PT-45 cancer cells were evaluated for selected compounds. Electrochemical investigation by cyclic voltammetry revealed that all bis-substituted metallocenes are up to 300 mV harder to oxidize compared to the monosubstituted 2-ferrocenylhexafluoropropan-2-ol (FcHFA: Delta E-0(f)=214 mV; disubstituted derivatives: up to Delta E-0(f) = 512 mV; both vs. FcH(0/+)). For the bis-substituted compounds, logP determinations by RP-HPLC showed increased lipophilicity in comparison to the monosubstituted FcHFA and RcHFA. Cellular uptake was investigated by fluorescence microcopy, and this revealed endosomal entrapment for 12.

We report the synthesis of trifluoromethylated metallocenes (M=Fe, Ru) and related metal-free compounds for comparison of their biological properties with the aim to establish structure-activity relationships toward the anti-proliferative activity of this compound class. All new compounds were comprehensively characterized by NMR spectroscopy (1H, 13C, 19F), mass spectrometry, IR spectroscopy, and elemental analysis. A single-crystal X-ray structure was obtained on the Ru derivative, 1-(1-hydroxy-1-hexafluoromethylethyl)ruthenocene (3). The cytotoxicity of all compounds was tested on MCF-7, HT-29, and PT-45 cells, and IC50 values as low as 12M were observed. Both the metallocene moiety and the hydroxy function are crucial for cytotoxicity. In addition, the activity decreased sharply even if only one trifluoromethyl group was replaced with a methyl group. Electrochemical investigations by cyclic voltammetry revealed that all CF3-containing compounds are harder to oxidize than the unsubstituted metallocenes. Moreover, logP determination by RP-HPLC showed the fluorinated derivatives to have higher lipophilicity, with logP values up to 4.6. At the same time, the generation of reactive oxygen species (ROS) in Jurkat cells by these compounds was investigated by flow cytometry. Strong ROS production was shown exclusively for the bis-CF3 derivative 1-(1-hydroxy-1-hexafluoromethylethyl)ferrocene (1) after 6 and 24h. Also on the Jurkat cell line, only compound 1 strongly induces necrosis after 24 and 48h, as shown by annexinV/propidium iodide staining. No induction of apoptosis was observed. We propose that compound 1 is more efficiently incorporated into cancer cells relative to all other derivatives, causing significant induction of oxidative stress within the cell, which ultimately leads to cell death.

We report the facile synthesis of four different trifluoromethylated metallocene triazoles and their biological evaluation (M = Fe and Ru). The cytotoxicity of all compounds was evaluated using MCF-7, HT-29, PT-45 and GM5657 cells and IC50 values as low as 33 μM were found. It was shown that the metallocene moiety is crucial for the cytotoxic effect. The electrochemical behavior of triazoles 3–6 was investigated by cyclic voltammetry. These electrochemical measurements revealed that all triazoles are less prone to oxidation than ferrocene. Moreover, Log P determination by RP-HPLC showed increased lipophilicity for the fluorinated derivatives with Log P values up to 3.8. Furthermore, successful bioconjugation could be achieved by coupling triazole 7 to the amino acid L-leucine.

Mono- and bis(trifluoromethylthio)-substituted and perfluorooctanesulfonylferrocene derivatives were prepared by nucleophilic substitution reactions on the ferrocene core Thus Hg(SCF3)(2) was activated in situ by Cu and used for nucleophilic displacement reactions of bromide. Trifluoromethylsulfonylferrocene was not accessible by this method. The reaction of lithioferrocene with trifuloromethylsulfonyl chloride gave chloroferrocene ill small yield, presumably due to the high lattice energy of solid LiF. On the other hand, the known trifluoromethylferrocene was obtained as the only isolable compound from the photochemical reaction of CF3SSCF3, with ferrocene. The same product was detected in small amounts in the reaction of chloromercuryferrocene with trifluoromethylsulfonyl chloride. It thus appears that most established methods for trifluoromethylation of purely organic compounds fail for ferrocene due to Concurring redox reactions. The new compounds have been comprehensively characterized by elemental analyses, NMR and IR spectroscopy, mass spectrometry, and electrochemistry. The SCF3 group appears to be almost as electron-withdrawing as a trifluoromethyl group oil the ferrocene core.

"One-pot" substitution of the twenty hydrogen atoms in pentagonal dodecahedrane (C(20)H(20)) by OH, F, Cl, and Br atoms is explored. Electrophilic insertion of oxygen atoms with DMDO and TFMDO as oxidizing reagents ended, far off the desired C(20)(OH)(20), in complex polyol mixtures (up to C(20)H(10)(OH)(10) decols, a trace of C(20)H(OH)(19)?). Perfluorination was successful in a NaF matrix but (nearly pure) C(20)F(20) could be secured only in very low yield. "Brute-force" photochlorination (heat, light, pressure, time) provided a mixture of hydrogen-free, barely soluble C(20)Cl(16) dienes in high yield and C(20)Cl(20) as a trace component. Upon electron-impact ionization of the C(20)Cl(16) material sequential loss of the chlorine atoms was the major fragmentation pathway furnishing, however, only minor amounts of chlorine-free C(20) (+) ions. "Brute-force" photobrominations delivered an extremely complex mixture of polybromides with C(20)HBr(13) trienes as the highest masses. The MS spectra exhibited exclusive loss of the Br substituents ending in rather intense singly, doubly, and triply charged C(20)H(4-0) (+(2+)(3+)) ions. The insoluble approximately C(20)HBr(13) fraction (C(20)Br(14) trienes as highest masses) obtained along a modified bromination protocol, ultimately allowed the neat mass selection of C(20) (-) ions. The C(20)Cl(16) dienes and C(20)H(0-3)Br(14-12) tri-/tetraenes, in spite of their very high olefinic pyramidalization, proved resistant to oxygen and dimerization (polymerization) but added CH(2)N(2) smoothly. Dehalogenation of the respective cycloaddition products through electron-impact ionization resulted in C(22-24)H(4-8) (+(2+)) ions possibly constituting bis-/tris-/tetrakis-methano-C(20) fullerenes or partly hydrogenated C(22), C(23), and C(24) cages.

N,N-Dimethylpentafluoroaniline enters easily into reactions with a mixture of nitric and sulphuric acids or nitric acid with conversion of the side chain. In the reactions with mixtures of HNO3 and H2SO4, the formation of N-nitroso-N-methyl and N-nitro-N-methylpentafluoroanilines is observed. The ratio of these products was found to depend on the ratio of the acids: the formation of N-nitro-N-methylpentafluoroaniline increases with the quantity of sulphuric acid; N-nitroso-N-methylpentafluoroaniline is obtained when only nitric acid is employed. N,N-Dimethylperfluoro-p-toluidine, N,N-dimethylperfluoro-2,4-xylidine, N,N-dimethylperfluoro-5-aminoindane undergo similar transformations. N-Nitroso derivatives were converted by a mixture of HNO3 and H2SO4, HNO3 or NO2BF4 into the corresponding N-nitro derivatives. Formation of the corresponding N-nitroso-N-methyl derivatives occurs when N,N-dimethylpentafluoroaniline, N,N-dimethylperfluoro-ptoluidine are treated with HNO2.(C) 2002 Elsevier Science B.V. All rights reserved.

ChemInformVolume 33, Issue 43 p. 66-66 Preparative Organic Chemistry Interaction of N,N-Dimethylperfluoroarylamines with Nitric and Nitrous Acids. Vyacheslav E. Platonov, Vorozhtsov Inst. Org. Chem., Sib. Branch Russ. Acad. Sci., Novosibirsk 630090, RussiaSearch for more papers by this authorAlois Haas, Vorozhtsov Inst. Org. Chem., Sib. Branch Russ. Acad. Sci., Novosibirsk 630090, RussiaSearch for more papers by this authorMeinolf Schelvis, Vorozhtsov Inst. Org. Chem., Sib. Branch Russ. Acad. Sci., Novosibirsk 630090, RussiaSearch for more papers by this authorMax Lieb, Vorozhtsov Inst. Org. Chem., Sib. Branch Russ. Acad. Sci., Novosibirsk 630090, RussiaSearch for more papers by this authorKira V. Dvornikova, Vorozhtsov Inst. Org. Chem., Sib. Branch Russ. Acad. Sci., Novosibirsk 630090, RussiaSearch for more papers by this authorOl'ga I. Osina, Vorozhtsov Inst. Org. Chem., Sib. Branch Russ. Acad. Sci., Novosibirsk 630090, RussiaSearch for more papers by this author Vyacheslav E. Platonov, Vorozhtsov Inst. Org. Chem., Sib. Branch Russ. Acad. Sci., Novosibirsk 630090, RussiaSearch for more papers by this authorAlois Haas, Vorozhtsov Inst. Org. Chem., Sib. Branch Russ. Acad. Sci., Novosibirsk 630090, RussiaSearch for more papers by this authorMeinolf Schelvis, Vorozhtsov Inst. Org. Chem., Sib. Branch Russ. Acad. Sci., Novosibirsk 630090, RussiaSearch for more papers by this authorMax Lieb, Vorozhtsov Inst. Org. Chem., Sib. Branch Russ. Acad. Sci., Novosibirsk 630090, RussiaSearch for more papers by this authorKira V. Dvornikova, Vorozhtsov Inst. Org. Chem., Sib. Branch Russ. Acad. Sci., Novosibirsk 630090, RussiaSearch for more papers by this authorOl'ga I. Osina, Vorozhtsov Inst. Org. Chem., Sib. Branch Russ. Acad. Sci., Novosibirsk 630090, RussiaSearch for more papers by this author First published: 19 May 2010 https://doi.org/10.1002/chin.200243066Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume33, Issue43October 29, 2002Pages 66-66 RelatedInformation

N-methyl- and N-butylperfluoroarylamines are transformed by HNO3 into N-nitro-N-methyl- and N-nitro-N-butylperfluoroarylamines. These reactions were used to synthesise N-nitro-N-methylpentafluoroaniline and its p-CF3, -CN, -C6F5 substituted derivatives, N-nitro-N-methylperfluoro-2,4-xylidine, N-nitro-N-methyl-4-aminotetrafluoropyridine, N-nitro-N-methyl-5-aminoperfluoroindane, N-nitro-N-methyl-2-aminoheptafluoronaphthalene, 4,4′-bis(N-nitro-N-methylamino)octafluorobiphenyl from 4,4′-bis(N-methylamino)octafluorobiphenyl, N-nitro-N-n-butylpentafluoroaniline, N-nitro-N-n-butylperfluoro-p-toluidine, N-nitro-N-n-butyl-4-aminotetrafluoropyridine and N-nitro-bis(perfluoro-p-tolyl)amine. Tetrafluoro-p-benzoquinone and heptafluoro-p-toluquinol were obtained from N-methylpentafluoroaniline and N-methylperfluoro-p-toluidine, respectively, under the action of a mixture of HNO3 and H2SO4. The X-ray crystal structure of N-nitro-N-methylperfluoro-p-toluidine was determined.

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A dramatic increase of the clearing temperatures of liquid crystals based on bis(cyclohexyl)ethane 1 by 50 to 70 K can be achieved by the perfluorination of the central ethylene link. Conformational analysis indicates that this effect is due to the increased rigidity of the mesogenic core structure and to the suppression of conformers with a bent shape. Materials based on bis(cylohexyl)tetrafluoroethane 2 might play a crucial role as materials for the next generation of active matrix LCDs with reduced power consumption.

The molecular structure and conformational properties of perfluorodimethyl trithiocarbonate, (CF3S)2CS, were studied by gas electron diffraction (GED), vibrational spectroscopy and quantum chemical calculations (HF, MP2 and B3PW91 with 6-31G∗ basis sets). From Raman spectra a composition of 60(10)% (syn,syn) and 40(10)% (syn,anti) conformers (ΔG0=0.2(2)kcalmol−1) was derived for the liquid state. Syn/anti describes the orientation of the S–CF3 bonds relative to the CS bond. The GED investigation resulted in a mixture of 84(12)% (syn,syn) and 16(12)% (syn,anti) conformers for the gas phase (ΔG0=1.0(5)kcalmol−1). The calculations predict energy differences between the two conformers from 0.4 (B3PW91) to 0.9 (HF)kcalmol−1. The predominant (syn,syn) form possesses a non-planar sulfur–carbon skeleton of C2 symmetry with the S–CF3 bonds rotated out of the CS3 plane (φ(SC–S–C)=32(4)°). The theoretical calculations predict a planar or nearly planar skeleton for the (syn,anti) conformer. All three computational methods reproduce bond lengths and bond angles very well.

The geometric structure and the conformational composition of 1,1,1-trifluoromethanesulfenylamine, CF3SNH2, were investigated by gas electron diffraction (GED) and microwave spectroscopy (MW). In the MW spectra transitions of two conformers were observed. Rotational constants of deuterated species demonstrated that the more intense transitions belong to the anti form (nitrogen lone pair antiperiplanar to S–C bond). From relative intensities and dipole moments an energy difference ΔE=E(syn)−E(anti)=1.1(1)kcalmol−1 was derived. A joint analysis of GED and MW data resulted in the following skeletal parameters (rz values with 2σ uncertainties): S–N=1.673(5)Å, S–C=1.836(5)Å and C–S–N=101.8(8)°. These parameters and the energy difference are well reproduced by B3PW91/6-31G* calculations.

The efficient synthesis of 2,2-bis[(trifluoromethyl)thio]acetaldehyde by acidic hydrolysis of 1-(N,N-diethylamino)-2,2-bis[(trifluoromethyl)thio]ethene is presented. The tautomeric equilibrium for the compound obtained is strongly shifted to enol form, so with silver nitrate in water solution a corresponding silver salt is formed that reacts with ethyl bromide to ethyl 2,2-[(trifluoromethyl)thio]vinyl ether. The enol reacts with amines to form respective enamines. IR, MS, 1H, 13C, and 19F NMR data for compounds synthesized are given to support their structure elucidation.

Trifluoromethanesulfenyl isocyanide 3 was synthesised by abstraction of water from N-trifluoromethylsultanylformamide 1, which was prepared from formamide and CF3SCI. The NMR (1H, 13C, and 10F), MS and IR of 1 and 3 are described.

The interactions of N -pentafluorophenylcarbonimidoyl dichloride, N -pentafluorophenylbenzimidoyl chloride and N -pentafluorophenyl (C-pentafluorophenyl) imidoyl chloride with the S-nucleophilic reagents thiourea, sodium N,N -diethyldithiocarbamate, thiocarbonyl difluoride and bis(trifluoromethyl)trithiocarbonate in the presence of CsF or AgSCF 3 , or thiophenol and polyfluorinated thiophenols in the presence of anhydrous K 2 CO 3 , were studied. Reactions with charged S-nucleophiles and with S-nucleophiles in the presence of a base proceeded with preservation of the N-C multiple bond in the reaction products. By varying the reaction conditions in the case of N -pentafluorophenylcar-bonimidoyl dichloride it was possible to substitute one or two chlorines and obtain mono- or di-thioimidates. When C 6 F 5 or SC 6 F 5 groups were present at the C atom of the N-C multiple bond, preferential substitution of the para -fluorine atom occurred. Semiempirical PM3 calculation data were used to explain the direction of these reactions. N -Pentafluorophenylcarbonimidoyl dichloride reacted with sodium N , N -diethyldithiocarbamate or thiourea to give pentafluorophenylisothiocyanate. Depending on the conditions of the reactions of polyfluorinated benzimidoyl chlorides with thiourea, N -pentafluorophenylthioamides and 2-aryl-4,5,6,7-tetrafluorobenzothiazoles were formed. An attempt to produce SCF 3 derivatives from AgSCF 3 was unsuccessful.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

5,5,5-trifluoro-4-trifluoromethyl-pent-3-en-2-one (1) and 5,5,5-trifluoro-4-methyl-pent-3-en-2-one (2) are reacted with a number of ring-substituted anilines to give the corresponding imines 3–16 and 17. The preparation of 2 is accompanied by three unsaturated ketones (2a–c). The bistrifluoromethylated imines 3–16 exist as a mixture of their non-separable syn and anti isomers, which were identified by 13C, 19F and 1H NMR spectroscopy. Some of these imines react with 2,2-bis(trifluoromethyl)-ethylene-1,1-carbodinitrile (BTF) at room temperature to 4,4-bistrifluoro-1,4-dihydropyridinium derivatives (18-22). Two side-products, 1-amino-cyclo-pent-l-ene (23–27) and 1-imino-cyclopent-2-ene derivatives (28–32) are also obtained in these additions. Treatment of 1 with primary alkylamines yielded the anti-Michael products 33–38. With 2-amino-benzylamine 1 formed the benzodiazepine derivative 39.

The geometric structure of trifluoromethyl vinyl sulfide, CF3SC(H)=CH2, was determined by gas electron diffraction and ab initio calculations (HF/3-21G* and MP2/6-31G*). A single conformer with a dihedral angle phi(C=C-S-C) = 129(4)degrees is present. The conformational properties are compared to those of the parent compound, CH3SC(H)=CH2, and of the perfluorinated species CF3SC(F)=CF2.