- Synthesis and electronic properties of ferrocene-containing organic dyads
-
Novel ferrocene-oligothiophenylene-cyanoacrylic acid in the form of donor-spacer-acceptor dyads was synthesized. The compound with a single unit of thiophenylene showed the lowest energy transition in neutral state. For radical cations, the lowest energy transition appears red-shifted along with the increased number of thiophenylene units. These results suggested that the electronic structure of radical cations is significantly different from that of neutral molecules.
- Watanabe, Motonori,Chang, Yuan Jay,Chou, Po-Ting,Staykov, Aleksandar,Shibahara, Masahiko,Sako, Katsuya,Ishihara, Tatsumi,Chow, Tahsin J.
-
-
Read Online
- Synthesis and electrochemical properties of a series of ferrocene-containing alcohols
-
A series of primary ferrocenylalcohols, Fc-(CH2)m-OH with m = 1-4 and Fc = ferrocenyl, was synthesised by reduction of the appropriate ferrocenylcarboxylic acids, Fc-(CH2)n-COOH (n = 0-3) and the ester methyl 4-ferrocenylbutanoate with LiAlH4, the reduction of the γ-ketoacid ferrocylpropanoic acid, Fc-CO-(CH 2)2-COOH, with AlCl3/LiAlH4, and the reduction of ferrocenylcarboxaldehyde, FcCHO, with NaBH4. The secondary ferrocenyl alcohols CpFe(C5H4-CH(OH)-CH 3) and Fe(C5H4-CH(OH)-CH3) 2 were obtained by NaBH4 reduction of acetyl and diacetyl ferrocene. The different reduction methods are compared. The electrochemistry of the alcohols was studied by cyclic voltammetry in CH3CN/0.1 M N(nBu)4PF6 utilising a platinum working electrode. The ferrocenyl group showed reversible electrochemistry with the formal reduction potential (Eo′ versus Fc/Fc+) of the ferrocenyl group inversely proportional to side chain length. The influence of the side chain length on Eo′ was more pronounced for the acids because the electron-withdrawing properties of the carbonyl group is stronger than that of the alcohol group. Ion pairing was found to play a major role in the electrochemical behaviour of ferrocenylmethanol, Fc-CH 2-OH.
- Davis, Wade L.,Shago, Rebotsamang F.,Langner, Ernie H.G.,Swarts, Jannie C.
-
-
Read Online
- Click-chemistry approach to synthesis of functionalized isatin-ferrocenes and their biological evaluation against the human pathogen Trichomonas vaginalis
-
Copper-promoted azide-alkyne cycloadditions were attempted to synthesize a series of variedly functionalized 1H-1,2,3-triazole-linked isatin-ferrocene, ferrocenylmethoxy-isatin and isatin-ferrocenyl-chalcone conjugates. The synthesized scaffolds were assayed for their inhibitory activity against T. vaginalis as well as several common normal human flora bacteria. The observed inhibitory activities against T. vaginalis and undetectable inhibition of microflora bacteria suggest that these compounds may be specific against trichomonad protozoa and could serve as a new scaffold for synthesis of novel compounds against this important human pathogen.
- Singh, Amandeep,Zhang, David,Tam, Christina C.,Cheng, Luisa W.,Land, Kirkwood M.,Kumar, Vipan
-
-
Read Online
- Electrochemical investigation on the polycondensation kinetics of silicon alkoxides by functionalization of the silica network by redox species
-
The sol-gel polycondensation of tetramethoxysilane has been followed for the first time by functionalization of the oligomeric silane species with a redox active ferrocene. Recording the decrease of the average diffusion coefficient of the mobile species brings information on the sol or gel state, as well as an easy insight of the polycondensation kinetics.
- Audebert,Sallard,Sadki
-
-
Read Online
- Formylation of a metathesis-derived: Ansa [4]-ferrocene: A simple route to anticancer organometallics
-
Formylation of ansa[4]-ferrocene, obtained through the ruthenium-catalysed olefin metathesis, yields two separable, planar chiral 1,3-and 1,2-ansa-ferrocene aldehydes. Single-crystal X-ray structure analysis reveals that both regioisomers crystallize with spontaneous resolution of the racemate in the chiral P212121 space group with one molecule in the asymmetric unit. The major 1,3-isomer was further transformed into a conjugate with 1,2,3-triazole and uracil using click chemistry as the key synthetic step. This inorganic-organic hybrid displays anticancer activity (MCF-7, A549, MDA-MB-231 cell lines) with EC50 values comparable to those for cisplatin.
- Bretner, Maria,Buchowicz, W?odzimierz,Kamiński, Rados?aw,Koszytkowska-Stawińska, Mariola,Mazur, Maria,Mrozowicz, Micha?,Ochal, Zbigniew,Wińska, Patrycja
-
-
Read Online
- Si(OCH2Fc)4: Synthesis, Electrochemical Behavior, and Twin Polymerization
-
The preparation and twin polymerization of the twin monomer Si(OCH2Fc)4 [Fc = Fe(η5-C5H4)(η5-C5H5)] (2) by the reaction of FcCH2OH (1) with SiCl4 in the presence of pyridine was explored. The electronic properties of 2 were investigated by cyclic voltammetry, square-wave voltammetry, and UV/Vis/near-IR spectroelectrochemistry, which showed a redox separation caused by electrostatic repulsion. Thermally induced condensation of 2 is characteristic, as evidenced by differential scanning calorimetry (DSC) and thermogravimetry coupled mass spectrometry (TG-MS). Upon heating 2 to 210 °C, twin polymerization occurred and a hybrid material was formed that showed similarities with known systems derived from 2,2′-spirobi[4H-1,3,2-benzodioxasiline] (SBS), such as the nanopatterning of the formed silicon dioxide, which is characteristic for twin polymerization. Electron microscopy of this material revealed the absence of typical microstructuring found for other twin polymers, and hence, the herein presented system can be characterized as a borderline system if compared to known twin monomers such as SBS. The copolymerization of 2 and SBS afforded a hybrid material from which porous carbon or silica materials containing iron oxide nanoparticles could be obtained. The oxidation state of the incorporated particles was examined by M?ssbauer experiments, which confirmed that only FeIII was incorporated within the porous carbon and silica materials, respectively. The preparation of iron oxide containing porous carbon capsules was achieved by applying a mixture of 2 and SBS to silicon dioxide spheres (d = 200 nm). After twin polymerization and carbonization, porous carbon capsules with incorporated iron oxide nanostructures were obtained. The straightforward preparation of iron-rich porous carbon and silica materials by twin polymerization of Si(OCH2Fc)4 [Fc = Fe(η5-C5H4)(η5-C5H5)] and 2,2′-spirobi[4H-1,3,2-benzodioxasiline] is reported; the electrochemical properties of Si(OCH2Fc)4 are discussed.
- Schliebe, Christian,Pfaff, Ulrike,Gemming, Thomas,Lochenie, Charles,Weber, Birgit,Lang, Heinrich
-
-
Read Online
- Synthesis of new ferrocenyl derivatives and their use in the first cyclopropanation of fullerene C60 with ferrocenes
-
New ferrocenyl derivatives (a β-ketoester and a β-diester) were synthesised and linked to fullerene C60, with the aim to elucidate factors involved in intramolecular electronic communication. These are the first examples of fullerene functionalised with ferrocenes via the cyclopropanation reaction. The resulting dyads were characterised.
- Floris, Barbara,Galloni, Pierluca,Seraglia, Roberta,Tagliatesta, Pietro
-
-
Read Online
- Electrocatalytic hydrocarbon hydroxylation by ethylbenzene dehydrogenase from Aromatoleum aromaticum
-
We report the electrocatalytic activity of ethylbenzene dehydrogenase (EBDH) from the β-proteobacterium Aromatoleum aromaticum. EBDH is a complex 155 kDa heterotrimeric molybdenum/iron-sulfur/heme protein which catalyzes the enantioselective hydroxylation of nonactivated ethylbenzene to (S)-1-phenylethanol without molecular oxygen as cosubstrate. Furthermore, it oxidizes a wide range of other alkyl-substituted aromatic and heterocyclic compounds to their secondary alcohols. Hydroxymethylferrocenium (FM) is used as an artificial electron acceptor for EBDH in an electrochemically driven catalytic system. Electrocatalytic activity of EBDH is demonstrated with both its native substrate ethylbenzene and the related substrate p-ethylphenol. The catalytic system has been modeled by electrochemical simulation across a range of sweep rates and concentrations of each substrate, which provides new insights into the kinetics of the EBDH catalytic mechanism.
- Kalimuthu, Palraj,Heider, Johann,Knack, Daniel,Bernhardt, Paul V.
-
-
Read Online
- Synthesis of esters of metallocene alcohols and 4,5-dichloroisothiazol-3-carboxylic and 5-arylisoxazole-3-carboxylic acids
-
Acylation of alkyl- and 1,1′-dialkylferrocene alcohols and diols as well as (3,4,4-trichlorobut-3-ene-1-ol-1-yl)-4,5-cymantrene with dichloroisothiazole- and 5-arylisoxazole-3-carbonyl chlorides has afforded esters containing 1,2-azoles fragments. Some of the obtained compounds have exhibited potentiating action in the binary mixtures with insecticides.
- Potkin,Dikusar,Kletskov,Petkevich,Semenova,Kolesnik,Zvereva,Zhukovskaya,Rosentsveig,Levkovskaya,Zolotar
-
-
Read Online
- Physicochemical properties of nitrogen-doped carbon nanotubes from metallocenes and ferrocenyl imidazolium compounds
-
Shaped carbon nanomaterials (SCNMs) were synthesized via the chemical vapour deposition (CVD) technique by using typical metallocenes (ferrocene, nickelocene, cobaltocene, and ruthenocene), and more interestingly, by use of novel ferrocenyl imidazolium derivatives, containing -Cl (FcImCl), -NO2 (FcImNO2) and -CH3 (FcImCH3) substituents as catalysts. Acetonitrile was applied both as a carbon and nitrogen source at temperatures 800–900 °C. The SCNMs, namely, carbon nanotubes (CNTs), carbon spheres (CS), carbon fibres (CF) and amorphous carbons (ACs) were obtained in varying ratios depending on the catalyst and carbon sources. The ferrocenyl imidazolium catalysts produced nitrogen-doped CNTs (N-CNTs) with bamboo-like structures. The yields of various reactions were temperature-dependent, with the highest amount of N-CNTs obtained at 850 °C. In all samples, the composition was mainly of CS and N-CNTs except for nickelocene at 800 °C that gave CFs as a “minor” product. Ferrocene and nickelocene in acetonitrile produced well-aligned N-CNTs while cobaltocene and ruthenocene gave 'spaghetti-like’ structures. In the case of ferrocenyl imidazolium catalyst, a coiled N-CNTs morphology was produced from FcImCl catalyst. Also, higher percentage of N-CNTs with traces of CS were obtained from the FcImCl and FcImCH3 catalysts in acetonitrile at 850 °C, while higher percentage of CS and AC were obtained for FcImNO2 catalyst. In all the catalysts, the use of acetonitrile promoted nitrogen-doping (samples with more disordered and with smaller outer-diameters). Thus, this study demonstrates that the synthesis of N-CNTs from nitrogen-containing ferrocenyl imidazolium compounds as catalyst sources, provided higher percentage of N-CNTs which can be suitable for various application.
- Labulo, Ayomide H.,Ngidi, Nonjabulo P.D.,Omondi, Bernard,Nyamori, Vincent O.
-
-
Read Online
- Reactions of ferrocenyl amines and alcohols with hexachlorocyclotriphosphazene
-
The reactions of ferrocenyl methanol, ferrocenyl 2-propanol and N-methyl-2-ferrocenylmethylamine with chlorocyclophosphazenes have been examined. The pentachlorocyclotriphosphazene derivative of ferrocenylmethanol undergoes rapid decomposition via a phosphazene-phosphazane rearrangement, however when the alcohol function is β to the cyclopentadienyl ring modest yields of N3P3Cl5OCHMeCH2C5H 4FeCp may be obtained. By way of contrast N-methyl-2-ferrocenylmethylamine gives a broad range of stable derivatives, N3P3Cl6-n[NMeCH2C5H 4FeCp]n(n=1-3). The substitution process follows a predominantly trans non-geminal pathway. The corresponding reaction with the butylmethacrylate derivative, N3P3Cl5O(CH2) 4OC(O)CMe=CH2 leads to the unexpected geminal product, 2,2′-N3P3Cl4[O(CH2) 4OC(O)CMe=CH2]NMeCH2C5H 4FeCp. Polymers containing the 2-ferrocenylmethylamine function have been obtained by reactions of poly(dichlorophosphazene) with the ferrocenylamine and by radical addition polymerization of the aforementioned mixed ferrocenylamino butylmethacrylphosphazene. The new materials have been characterized by standard methologies including 31P NMR spectroscopy, cyclic voltametry and gel permeation chromatography.
- Allen, Christopher W.,Myer, Charles N.
-
-
Read Online
- MOESSBAUER STUDIES ON FERROCENE COMPLEXES. III. STRUCTURE OF FERROCENYL CARBENIUM IONS
-
Moessbauer and NMR spectra are reported for ferrocenyl (Fc) carbenium ions, FcCH2+ (III+) and FcC+Me2 (II+) in frozen acidic media. 1H-NMR spectra showed no evidence of Fe-H bonded species.Moessbauer parameters
- Neshvad, G.,Roberts, R.M.G.,Silver, J.
-
-
Read Online
- Activation by Oxidation: Ferrocene-Functionalized Ru(II)-Arene Complexes with Anticancer, Antibacterial, and Antioxidant Properties
-
Organometallic Ru(II)-cymene complexes linked to ferrocene (Fc) via nitrogen heterocycles have been synthesized and studied as cytotoxic agents. These compounds are analogues of Ru(II)-arene piano-stool anticancer complexes such as RAPTA-C. The Ru center was coordinated by pyridine, imidazole, and piperidine with 0-, 1-, or 2-carbon bridges to Fc to give six bimetallic, dinuclear compounds, and the properties of these complexes were compared with their non-Fc-functionalized parent compounds. Crystal structures for five of the compounds, their Ru-cymene parent compounds, and an unusual trinuclear compound were determined. Cyclic voltammetry was used to determine the formal MIII/II potentials of each metal center of the Ru-cymene-Fc complexes, with distinct one-electron waves observed in each case. The Fc-functionalized complexes were found to exhibit good cytotoxicity against HT29 human colon adenocarcinoma cells, whereas the parent compounds were inactive. Similarly, antibacterial activity from the Ru-cymene-Fc compounds was observed against Bacillus subtilis, but not from the unfunctionalized complexes. In both cases, the IC50 values correlated quantitatively with the Fc+/0 reduction potentials. This is consistent with more facile oxidation to give ferrocenium, and subsequent generation of toxic reactive oxygen species, leading to greater cytotoxicity. The antioxidant properties of the complexes were quantified by a 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay. EC50 values indicate that linking of the Ru and Fc centers promotes antioxidant activity.
- Mu, Changhua,Prosser, Kathleen E.,Harrypersad, Shane,Macneil, Gregory A.,Panchmatia, Rikesh,Thompson, John R.,Sinha, Soumalya,Warren, Jeffrey J.,Walsby, Charles J.
-
-
Read Online
- Influence of methylimidazole isomers on ferrocene-catalysed nitrogen doped carbon nanotube synthesis
-
Nitrogen doped multi-walled carbon nanotubes (N-CNTs) were synthesized by the solid state pyrolysis of ferrocenylmethylimidazole or a mixture of ferrocene (FcH)/i-methylimidazole (i = 1, 2 and 4) at 800 °C at different ratios in sealed quartz tubes. Transmission electron microscopy (TEM) images confirmed that the carbon nanotubes (CNTs) obtained were doped with nitrogen to give nitrogen doped multi-walled CNTs (N-CNTs). N-CNTs showed bamboo-like structures for the CNTs produced from both ferrocenylmethylimidazole and the mixtures of FcH/i-methylimidazole at varying ratios. The study revealed that the different imidazoles produced different types/size distributions of shaped carbon nanomaterials (SCNMs) including N-CNTs with different diameters. An investigation of the bamboo structures revealed that the three methylimidazole isomers led to tubes with different individual bamboo compartment distances and different morphologies including different N contents. This confirms that the synthesis of N-CNTs is determined by fragments (ratios, types) produced by decomposition of reactants at high temperature.
- Nxumalo, Edward N.,Chabalala, Vongani P.,Nyamori, Vincent O.,Witcomb, Michael J.,Coville, Neil J.
-
-
Read Online
- A Stable Primary Phosphane Oxide and Its Heavier Congeners
-
(Ferrocenylmethyl)phosphane (1) oxidation with hydrogen peroxide, elemental sulfur and grey selenium produced (ferrocenylmethyl)phosphane oxide 1O, sulfide 1S and selenide 1Se, respectively, as the first isolable primary phosphane chalcogenides lacking steric protection. At elevated temperatures, compound 1O disproportionated into 1 and (ferrocenylmethyl)phosphinic acid. In reactions with [(η6-mes)RuCl2]2, 1O underwent tautomerization into a phosphane complex [(η6-mes)RuCl2{FcCH2PH(OH)-κP}], whereas 1S and 1Se lost their P-bound chalcogen atoms, giving rise to the phosphane complex [(η6-mes)RuCl2(FcCH2PH2-κP)] (Fc=ferrocenyl, mes=mesitylene). No tautomerization was observed in the reaction of 1O with B(C6F5)3, which instead produced a Lewis pair FcCH2P(O)H2-B(C6F5)3. Phosphane oxide 1O added to C=O bonds of aldehydes and ketones and even to cumulenes PhNCE (E=O and S). However, both PH hydrogens were only employed in the reactions with aldehydes and cyanates.
- Horky, Filip,Císa?ová, Ivana,?těpni?ka, Petr
-
-
Read Online
- Light-Triggered Metal Coordination Dynamics in Photoswitchable Dithienylethene-Ferrocene System
-
The C2-symmetric photochromic molecule 3, containing dithienylethene (DTE) and ferrocene units connected by an alkyne bridge, represents a unique probe where a metal (Hg2+) binds with the central DTE moiety. Both photoisomerized states of 3 (open, 3o; closed, 3c) are found to interact with Hg2+ ion by the S atoms of the DTE core; however, the binding constants (from a UV-vis study) and DFT calculations suggest that the open isomer (3o) binds with the metal ion more strongly than that of the closed isomer (3c). Notably, the course of metal binding does not perturb the inherent photoisomerization properties of the DTE core and the photoswitchability persists even in the metal-coordinated form of 3, however, with a comparatively slower rate. The quantum yields for photocyclization (φo→c) and photocycloreversion (φc→o) in the free form are 0.56 and 0.007, respectively, whereas the photocyclization quantum yield in the Hg2+ complexed species is 0.068, 8.2 times lower than the photocyclization quantum yield (φo→c) of free 3o. Thus, the rate of photoisomerization can be modulated by a suitable metal coordination to the DTE core. The dynamics of photoswitchability in the metal-coordinated form of DTE has been explored by experimental means (UV-vis and electrochemical studies) as well as quantum chemical calculations.
- Adarsh, Nayarassery N.,Karmakar, Manisha,Mondal, Bijan,Pal, Adwitiya,Thakur, Arunabha
-
supporting information
p. 6086 - 6098
(2021/05/06)
-
- A Bifunctional Copper Catalyst Enables Ester Reduction with H2: Expanding the Reactivity Space of Nucleophilic Copper Hydrides
-
Employing a bifunctional catalyst based on a copper(I)/NHC complex and a guanidine organocatalyst, catalytic ester reductions to alcohols with H2 as terminal reducing agent are facilitated. The approach taken here enables the simultaneous activation of esters through hydrogen bonding and formation of nucleophilic copper(I) hydrides from H2, resulting in a catalytic hydride transfer to esters. The reduction step is further facilitated by a proton shuttle mediated by the guanidinium subunit. This bifunctional approach to ester reductions for the first time shifts the reactivity of generally considered "soft"copper(I) hydrides to previously unreactive "hard"ester electrophiles and paves the way for a replacement of stoichiometric reducing agents by a catalyst and H2.
- Kaicharla, Trinadh,Ngoc, Trung Tran,Teichert, Johannes F.,Tzaras, Dimitrios-Ioannis,Zimmermann, Birte M.
-
supporting information
p. 16865 - 16873
(2021/10/20)
-
- Azide-alkyne cycloaddition en route to ferrocenyl-methoxy-methyl-isatin-conjugates: Synthesis, anti-breast cancer activities and molecular docking studies
-
A series of 1H-1,2,3-triazole linked Ferrocenyl-methoxy-methyl-Isatin conjugates was synthesized and assayed for their anti-proliferative activities against estrogen-responsive as well as estrogen non-responsive cell lines. The non-cytotoxic conjugate 7l, with an optimum combination of octyl chain as spacer and methyl-substituent at the C-5 position of isatin, proved to be a promising hit with an IC50 value of 14.62 μM against MCF-7 and 79.63 μM against MDA-MB-231 cells, respectively. The observed anti-proliferative activities of active conjugates were further corroborated via docking studies carried out on estrogen receptor subtypes α and β.
- Rani, Anu,Singh, Gurjot Inder,Kaur, Ramandeep,Palma, Gabriella,Perumal, Shanen,Kaur, Mandeep,Ebenezer, Oluwakemi,Awolade, Paul,Singh, Parvesh,Kumar, Vipan
-
-
- Lithium Bromide/HBpin: A Mild and Effective Catalytic System for the Selective Hydroboration of Aldehydes and Ketones
-
The catalytic hydroboration of aldehydes and ketones with HBpin was examined using simple and commercially available metal salts (Li, Na, and K). Among the tested salts, LiBr (0.5–1.0 mol%) was found to be an efficient catalyst for the hydroboration of various aldehydes and ketones at room temperature. Further, the chemoselective hydroboration of aldehydes over ketones was also demonstrated.
- An, Duk Keun,Choi, Hyeon Seong,Hwang, Hyonseok,Kim, Hanbi,Lee, Ji Hye,Shin, Hye Lim,Yi, Jaeeun
-
p. 1009 - 1018
(2020/10/12)
-
- A convenient method for synthesis of novel alkylferrocene derivatives with various functional groups: synthesis, characterization and electrochemical investigation
-
Abstract: In this research, new ferrocenylmethylesters were synthesized according to esterification reaction. To reach this purpose, direct and indirect esterification methods were used. Indirect method included Cannizzaro reaction of new alkylferrocenecarboxaldehydes result in production of alkylferrocenecarboxylic acids and alkyl(hydroxymethyl)ferrocene derivatives. Finally, a variety of known procedures were used for converting the new alkylferrocenecarboxylic acids to the corresponding esters. The oxidative esterification reaction was accomplished using K2CO3/I2 as oxidant in the direct method. The advantages of this method are one-pot and single-step reaction and remarkably high total yield of this procedure. The chemical structures were confirmed with FT-IR, 1H NMR, 13C NMR and MASS spectroscopy as well as CHN analysis. Electrochemical behavior of synthesized compounds was studied by cyclic voltammetry, and the relationship between the peak currents and the square root of the scan rate showed that the redox process is diffusion-limited. Graphic abstract: [Figure not available: see fulltext.].
- Teimuri-Mofrad, Reza,Aghaiepour, Alireza,Rahimpour, Keshvar
-
p. 2449 - 2462
(2020/05/06)
-
- Homogeneous Hydrogenation with a Cobalt/Tetraphosphine Catalyst: A Superior Hydride Donor for Polar Double Bonds and N-Heteroarenes
-
The development of catalysts based on earth abundant metals in place of noble metals is becoming a central topic of catalysis. We herein report a cobalt/tetraphosphine complex-catalyzed homogeneous hydrogenation of polar unsaturated compounds using an air- and moisture-stable and scalable precatalyst. By activation with potassium hydroxide, this cobalt system shows both high efficiency (up to 24 000 TON and 12 000 h-1 TOF) and excellent chemoselectivities with various aldehydes, ketones, imines, and even N-heteroarenes. The preference for 1,2-reduction over 1,4-reduction makes this method an efficient way to prepare allylic alcohols and amines. Meanwhile, efficient hydrogenation of the challenging N-heteroarenes is also furnished with excellent functional group tolerance. Mechanistic studies and control experiments demonstrated that a CoIH complex functions as a strong hydride donor in the catalytic cycle. Each cobalt intermediate on the catalytic cycle was characterized, and a plausible outer-sphere mechanism was proposed. Noteworthy, external inorganic base plays multiple roles in this reaction and functions in almost every step of the catalytic cycle.
- Duan, Ya-Nan,Du, Xiaoyong,Cui, Zhikai,Zeng, Yiqun,Liu, Yufeng,Yang, Tilong,Wen, Jialin,Zhang, Xumu
-
supporting information
p. 20424 - 20433
(2019/12/27)
-
- Ferrocene-appended iridium(III) Complexes: Configuration regulation, anticancer application, and mechanism research
-
A series of ferrocene-appended half-sandwiched iridium(III) phenylpyridine complexes have been designed and synthesized. These complexes show better anticancer activity than cisplatin widely used in clinic under the same conditions. Meanwhile, complexes could effectively inhibit cell migration and colony formation. Complexes could interact with protein and transport through serum protein, effectively catalyzing the oxidation of nicotinamide-adenine dinucleotid and inducing the accumulation of reactive oxygen species (ROS, 1O2), which confirmed the anticancer mechanism of oxidation. Furthermore, laser scanning confocal detection indicates that these complexes can enter cells followed by a non-energy-dependent cellular uptake mechanism, effectively accumulating in the lysosome (Pearson's colocalization coefficient: ~0.90), leading to lysosome damage, and reducing the mitochondrial membrane potential (MMP). Taken together, ferrocene-appended iridium(III) complexes possess the prospect of becoming a new multifunctional therapeutic platform, including lysosome-targeted imaging and anticancer drugs.
- Ge, Xingxing,Chen, Shujiao,Liu, Xicheng,Wang, Qinghui,Gao, Lijun,Zhao, Chengfeng,Zhang, Lei,Shao, Mingxiao,Yuan, Xiang-Ai,Tian, Laijin,Liu, Zhe
-
p. 14175 - 14184
(2019/10/16)
-
- Controlled Reduction of Carboxamides to Alcohols or Amines by Zinc Hydrides
-
New protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination of sodium hydride (NaH) and zinc halides (ZnX2). Use of a different halide on ZnX2 dictates the selectivity, wherein the NaH-ZnI2 system delivers alcohols and NaH-ZnCl2 gives amines. Extensive mechanistic studies by experimental and theoretical approaches imply that polymeric zinc hydride (ZnH2)∞ is responsible for alcohol formation, whereas dimeric zinc chloride hydride (H?Zn?Cl)2 is the key species for the production of amines.
- Ong, Derek Yiren,Yen, Zhihao,Yoshii, Asami,Revillo Imbernon, Julia,Takita, Ryo,Chiba, Shunsuke
-
supporting information
p. 4992 - 4997
(2019/03/13)
-
- A ferrocene-containing group of the carbamate compound and its synthesis method
-
The invention discloses a carbamate compound containing a ferrocene group and a synthesis method thereof, and belongs to the macromolecule field. The invention also discloses a preparation method of the carbamate compound containing the ferrocene group. The carbamate compound containing the ferrocene group has good chemical property stability and has various catalytic properties; the carbamate compound is used in a lubricating oil additive, and besides, has good oxidation resistance, abrasion resistance and corrosion resistance; and the carbamate compound is used in a fuel additive, and has the advantages of suppressing smoke, supporting combustion and reducing pollution.
- -
-
Paragraph 0033; 0038; 0043
(2018/02/04)
-
- Cyclopentadienyl-ruthenium(II) complexes as efficient catalysts for the reduction of carbonyl compounds
-
This work reports the reduction of a large variety of aldehydes and ketones with the system PhSiH3/[CpRu(PPh3)2Cl] in good to excellent yields and high chemoselectivity. The catalyst [CpRu(PPh3)2Cl] can be used in at least 12 catalytic cycles with excellent catalytic activity and several substrates were reduced under solvent free conditions.
- Cabrita, Ivania R.,Florindo, Pedro R.,Fernandes, Ana C.
-
p. 1511 - 1516
(2017/02/18)
-
- α-Amino Aldehydes as Readily Available Chiral Aldehydes for Rh-Catalyzed Alkyne Hydroacylation
-
Readily available α-amino aldehydes, incorporating a methylthiomethyl (MTM) protecting group on nitrogen, are shown to be efficient substrates in Rh-catalyzed alkyne hydroacylation reactions. The reactions are performed under mild conditions, employing a small-bite-angle bis-phosphine ligand, allowing for good functional group tolerance with high stereospecificity. Amino aldehydes derived from glycine, alanine, valine, leucine, phenylalanine, isoleucine, serine, tryptophan, methionine, and cysteine were successfully employed, as was an enantiomerically enriched α-OMTM-aldehyde derived from phenyllactic acid. The synthetic utility of the α-amino enone products is demonstrated in a short enantioselective synthesis of the natural product sphingosine.
- Hooper, Joel F.,Seo, Sangwon,Truscott, Fiona R.,Neuhaus, James D.,Willis, Michael C.
-
supporting information
p. 1630 - 1634
(2016/02/20)
-
- A PHOTO-CLEAVABLE MASS TAG AND USE OF THE SAME
-
The present invention refers to photo-degradable relates to of the present invention and use thereof markers mass markers mass photo-degradable biomarker-of detecting and quantifying analysis may be utilized, multiple marker synchronous detection of ID. (by machine translation)
- -
-
Paragraph 0052; 0054; 0061; 0062
(2016/10/07)
-
- A DFT-Elucidated comparison of the solution-phase and SAM electrochemical properties of short-chain mercaptoalkylferrocenes: Synthetic and spectroscopic aspects, and the structure of Fc- CH2CH2-S-S-CH2CH2-Fc
-
Facile synthetic procedures to synthesize a series of difficult-To-obtain mercaptoalkylferrocenes, namely, Fc(CH2)nSH, where n = 1 (1), 2 (2), 3 (3), or 4 (4) and Fc = Fe(n5-C5H5)(n5-C5H4), are reported. Dimerization of 1-4 to the corresponding disulfides 19-22 was observed in air. Dimer 20 (Z = 2) crystallized in the triclinic space group Pi. Dimers 20-22 could be reduced back to the original Fc(CH2)nSH derivatives with LiAlH4 in refluxing tetrahydrofuran. Density functional theory (DFT) calculations showed that the highest occupied molecular orbital of 1-4 lies exclusively on the ferrocenyl group implying that the electrochemical oxidation observed at ca. -15 pa a radical, Fc(CH2)nS, with spin density mainly located on the sulfur. Rapid exothermic dimerization leads to the observed dimers, Fc(CH2)n-S-S- (CH 2)nFc. Reduction of the ferrocenium groups on the dimer occurs at potentials that still showed the ferrocenyl group E = Epa,monomer - Epc,dimer ≤ 78 mV, indicating that the redox properties of the ferrocenyl group on the mercaptans are very similar to those of the dimer. 1H NMR measurements showed that, like ferrocenyl oxidation, the resonance position of the sulfhydryl proton, SH, and others, are dependent on -(CH2)n- chain length. Self-Assembled monolayers (SAMs) on gold were generated to investigate the electrochemical behavior of 1-4 in the absence of diffusion. Under these conditions, δE approached 0 mV for the longer chain derivatives at slow scan rates. The surface-bound ferrocenyl group of the metal-Thioether, Fc(CH)n -S-Au, is oxidized at approximately equal potentials as the equivalent CH2Cl2-dissolved ferrocenyl species 1-4. Surface coverage by the SAMs is dependent on alkyl chain length with the largest coverage obtained for 4, while the rate of heterogeneous electron transfer between SAM substrate and electrode was the fastest for the shortest chain derivative, Fc-CH2-S-Au.
- Lewtak, Jan P,Landman, Marilé,Fernández, Israel,Swarts, Jannie C
-
p. 2584 - 2596
(2017/01/16)
-
- Unexpected acid-catalyzed ferrocenylmethylation of diverse nucleophiles with vinyloxymethylferrocene
-
A new efficient approach for the ferrocenylmethylation of various alcohols, OH-, SH- and SeH-acids (carboxylic, thio- and selenophosphinic) as well as 1H-triazoles is elaborated based on the acid-catalyzed reaction with available vinyloxymethylferrocene.
- Oparina, Ludmila A.,Artem'ev, Alexander V.,Vysotskaya, Oksana V.,Tarasova, Olga A.,Shagun, Vladimir A.,Bagryanskaya, Irina Yu.,Trofimov, Boris A.
-
p. 4414 - 4422
(2016/07/06)
-
- LABELLING COMPOUNDS AND THEIR USE IN ASSAYS
-
The invention provides monoferrocenyl compounds of general formula (I). The invention also provides substrates labelled with the compounds, functionalised derivatives of the compounds and methods of using the compounds, functionalised derivatives and labelled substrates in electrochemical assays.
- -
-
Page/Page column 18
(2015/04/28)
-
- An unprecedented deoxygenation protocol of benzylic alcohols using bis(1-benzotriazolyl)methanethione
-
A facile and regioselective two-step protocol for the deoxygenation of benzylic alcohols using bis(benzotriazole)methanethione has been devised. Benzotriazole derivatives, namely, benzyloxythioacylbenzotriazoles (ROCSBt), on reaction with silanes or Bu3SnH under microwave irradiation or conventional heating undergo a free radical β-scission of C-O bond instead of N-N bond (benzotriazole ring cleavage) to afford a deoxy product. The methodology has various applications because it selectively deoxygenates benzylic alcohols with the aid of a relatively nontoxic (TMS)3SiH reagent as an acceptable alternate to Bu3SnH.
- Kumar, Dhananjay,Singh, Anoop S.,Tiwari, Vinod K.
-
p. 31584 - 31593
(2015/04/22)
-
- Signal transduction and amplification through enzyme-triggered ligand release and accelerated catalysis
-
Signal transduction and signal amplification are both important mechanisms used within biological signalling pathways. Inspired by this process, we have developed a signal amplification methodology that utilises the selectivity and high activity of enzymes in combination with the robustness and generality of an organometallic catalyst, achieving a hybrid biological and synthetic catalyst cascade. A proligand enzyme substrate was designed to selectively self-immolate in the presence of the enzyme to release a ligand that can bind to a metal pre-catalyst and accelerate the rate of a transfer hydrogenation reaction. Enzyme-triggered catalytic signal amplification was then applied to a range of catalyst substrates demonstrating that signal amplification and signal transduction can both be achieved through this methodology.
- Goggins, Sean,Marsh, Barrie J.,Lubben, Anneke T.,Frost, Christopher G.
-
p. 4978 - 4985
(2015/07/27)
-
- Synthesis and characterization of new ferrocene-containing ionic liquids
-
A series of several new families of ferrocene-containing imidazolium salts were synthesized by etherification of ferrocene methanol, acylation of ferrocene, and amide coupling of ferrocene carboxylic acid. The etherification was achieved by an acid-catalyzed procedure and very good yields of between 86-93-% were obtained. Next to the nature of the linkage itself, the lengths of the alkyl chains linking the ferrocenyl moiety and the imidazolium group and the nature of the counterions were also varied. Interestingly, a γ-effect can be observed for the ether compounds but this effect was only visible in 13C NMR spectroscopy. These new redox-active ionic liquids were fully characterized by FTIR, 1H, 19F, and 13C NMR spectroscopy, and by MS, HRMS and elemental analysis. A novel series of ferrocenated ionic liquids with different spacer species between the ferrocenyl moiety and the imidazolium group have been developed. The spacer units have been established by amide coupling, etherification and acylation. The latter reaction is strongly influenced by the chain length of the acid chloride and a γ-effect is observable for the ether compounds. Copyright
- Gharib, Bhasem,Hirsch, Andreas
-
supporting information
p. 4123 - 4136
(2014/07/08)
-
- Direct trifluoromethylthiolation of alcohols under mild reaction conditions: Conversion of R-OH into R-SCF3
-
A direct process for the trifluoromethylthiolation of allylic and benzylic alcohols under mild conditions has been developed. A wide range of free alcohols underwent nucleophilic substitution in the presence of stable CuSCF3 and BF3·Et2O to give the corresponding products in good to excellent yields.
- Nikolaienko, Pavlo,Pluta, Roman,Rueping, Magnus
-
supporting information
p. 9867 - 9870
(2014/08/18)
-
- Application of ferrocenylimidazolium salts as catalysts for the transfer hydrogenation of ketones
-
Ferrocenylimidazolium salts with methylene and phenyl groups bridging the ferrocenyl and alkylimidazolium moieties were synthesized and characterized by spectroscopic and analytical methods. Crystal structures of two new compounds are also reported. Cyclic voltammetry was used to analyze the influence of the two bridging groups or spacers on electrochemical properties of the salts relative to the shifts in the formal electrode or peak potentials (E0 or E1/2) of the ferrocene/ferrocenium redox couple. Results from this study showed that all the salts exhibited higher electrode potentials relative to ferrocene, which is due to the electron-withdrawing effect of the imidazolium ion on the ferrocenyl moiety. Application of the salts as catalysts in transfer hydrogenation of ketones resulted in high conversion of saturated ketones to corresponding alcohols and turnover numbers as high as 1880. The catalysts were chemoselective towards reduction of the C=C bonds of conjugated 3-penten-2-one and 4-hexen-3-one to yield saturated ketones, while unconjugated 5-hexen-2-one was hydrogenated to an unsaturated alcohol. Copyright
- Ikhile, Monisola I.,Bala, Muhammad D.,Nyamori, Vincent O.,Ngila, J. Catherine
-
-
- A convenient nickel-catalysed hydrosilylation of carbonyl derivatives
-
Hydrosilylation of aldehydes and ketones catalysed by nickel acetate and tricyclohexylphosphine as the catalytic system was demonstrated using polymethylhydrosiloxane as a cheap reducing reagent. The Royal Society of Chemistry 2013.
- Zheng, Jianxia,Darcel, Christophe,Sortais, Jean-Baptiste
-
-
- Synthesis and biological evaluation of novel ferrocene-naphthoquinones as antiplasmodial agents
-
This work deals with the synthesis and evaluation of new compounds designed by combination of 1,4-naphthoquinone and ferrocene fragments in a 3-ferrocenylmethyl-2-hydroxy-1,4-naphthoquinone arrangement. A practical coupling reaction between 2-hydroxy-1,4-naphthoquinone and ferrocenemethanol derivatives has been developed. This procedure can be carried out "on-water", at moderate temperatures and without auxiliaries or catalysts, with moderate to high yields. The synthesized derivatives have shown significant in vitro antiplasmodial activity against chloroquine-sensitive and resistant Plasmodium falciparum strains and it has been shown that this activity is not related to the inhibition of biomineralization of ferriprotoporphyrin IX. Binding energy calculations and docking of these compounds to cytochrome b in comparison with atovaquone have been performed.
- García-Barrantes, Pedro M.,Lamoureux, Guy V.,Pérez, Alice L.,García-Sánchez, Rory N.,Martínez, Antonio R.,San Feliciano, Arturo
-
p. 548 - 557
(2013/12/04)
-
- Hydrosilylation of aldehydes and ketones catalyzed by an n-heterocyclic carbene-nickel hydride complex under mild onditions
-
Half-sandwich N-heterocyclic carbene (NHC)-nickel complexes of the general formula [NiACHTUNGTRENUNG(NHC)ClCp?] (Cp?= Cp, Cp*) efficiently catalyze the hydrosilylation of aldehydes and ketones at room temperature in the presence of a catalytic amount of sodium triethylborohydride and thus join the fairly exclusive club of well-defined nickel(II) catalyst precursors for the hydrosilylation of carbonyl functionalities. Of notable interest is the isolation of an intermediate nickel hydride complex that proved to be the real catalyst precursor.
- Bheeter, Linus P.,Henrion, Mickael,Brelot, Lydia,Darcel, Christophe,Chetcuti, Michael J.,Sortais, Jean-Baptiste,Ritleng, Vincent
-
supporting information
p. 2619 - 2624
(2013/01/15)
-
- Specific features of oxidation of ferrocenylacetic acid with molecular oxygen in the absence and in the presence of Bronsted acids
-
Comparative analysis of the specific features of autooxidation of ferrocenylacetic acid (FcCH2COOH) in organic solvents at 30-50°C in the absence and in the presence of trifluoroacetic acid (processes 1 and 2 respectively) was carried out. It w
- Fomin,Shirokov
-
p. 2304 - 2316
(2010/04/29)
-
- (η6-Arene)tricarbonylchromium and ferrocene complexes linked to binaphthyl derivatives
-
Palladium-catalyzed coupling reactions of 6,6′-dihydroxyboron-2, 2′-dimethoxy-1,1′-binaphthyl 5g and chloroarenetricarbonylchromium complexes 6a - c afforded complexes 7a - c with the binaphthyl residue directly linked to the (η6-arene)tricarbonylcriromium entity. Coupling reactions of 2,2′-dimethoxy, 3,3′diodo, and 6,6′-diodo-1, 1′-binaphthyl 3h and 5h with ethynylarenetricarbonylchromium derivatives 6d - f and ethynylferrocene 9 yielded binaphthyl compounds linked to arenetricarbonylchromium and feirocenyl derivatives 8a - c, 11a - c, 10, and 12 through a triple bond. Condensation of 2,2′-dimethylrriethoxy, 3-formyl, 1,1′-binaphthyl 2a with (η6-phenyl) methyltriphenylphosphonium tricarbonylchromium 13 and ferrocenylmethyltriphenylphosphonium 18 gave binaphthyl compounds linked to arenetricarbonylchromium and ferrocenyl derivatives 14 and 19, respectively, through a double bond. X-ray analyses of the dinuclear chromium complex 8a and of the mononuclear chromium complex 17-Z are described.
- Germaneau, Romain,Chavignon, Rene,Tranchier, Jean-Philippe,Rose-Munch, Francoise,Rose, Eric,Collot, Mayeul,Duhayon, Carine
-
p. 6139 - 6149
(2008/10/09)
-
- THE APPLICATION USING NON-COVALENT BOND BETWEEN A CUCURBITURIL DERIVATIVE AND A LIGAND
-
Provided are a kit including a first component that is a compound of formula (1) below bound to a first material and a second component that is a ligand bound to a second material, wherein each of the first and second materials is independently selected from the group consisting of a solid phase, a biomolecule, an antioxidant, a chemical therapeutic agent, an anti-histaminic agent, a cucurbituril dendrimer, a cyclodextrin derivative, a crown ether derivative, a calixarene derivative, a cyclophane derivative, a cyclic peptide derivative, a metallic ion, a chromophore, a fluorescent material, a phosphor, a radioactive material, and a catalyst; and the ligand can non-covalently bind to the compound of formula (1); a method of separating and purifying a material bound to a ligand using the compound of formula (1) bound to a solid phase; a method of separating and purifying the compound of formula (1) or a material bound to the compound using a ligand bound to a solid phase; a sensor chip including a compound of formula (1) bound to a first material and a ligand bound to a second material; and a solid-catalyst complex including the compound of formula (1) bound to a first material and a ligand bound to a second material.
- -
-
Page/Page column 20
(2010/11/27)
-
- α-Ferrocenylation of Tetrazole and Its 1-substituted Derivatives in Two-Phase Systems
-
Reactions of α-ferrocenylalkyl alcohols with tetrazole and its 1-substituted derivatives in two-phase systems of methylene chloride-aqueous solutions of HX acids (X = BF4, ClO4) result in the formation of 4-α-ferrocenylalkylated tetrazolium salts as the only isomers. Under the action of alkali reagents in aqueous media monosubstituted tetrazolium salts are converted into mixtures of 1- and 2-α-ferrocenylalkyl tetrazole derivatives, while disubstituted salts decompose to give the starting compounds when heated in 10% aqueous solution of sodium hydroxide. In the anhydrous medium, heating of 1-phenyl-5-ferrocenylmethylenetetrazolium fluoborate with t-BuOK in dioxane results in a rearrangement which proceeds by an ilide-type mechanism to form 1-phenyl-5-ferrocenylmethylenetetrazole. The latter reacts in the two-phase system with ferrocenylmethanol to give the corresponding trisubstituted tetrazolium salt.
- Boev,Krasnikova,Moskalenko,Pil'ko,Snegur,Babin,Nekrasov
-
p. 1299 - 1305
(2007/10/03)
-
- Synthese und Reaktivitaet von Ferrocenyl-Pentacarbonylmangan, Mn(CO)5Fc
-
The compound Mn(CO)5Fc can be prepared by the reaction of Mn(CO)5Br with ferrocenyllithium, FcLi.The mangana-β-diketone H, obtained as a side-product, is converted into Mn(CO)5Fc with concomitant formation of diferrocenoyl, (FcCO)2.In prot
- Herberhold, Max,Kniesel, Heidemarie
-
p. 347 - 358
(2007/10/02)
-
- Ferrocenylmethyl azide
-
The preparation of ferrocenylmethyl azide and its use as a synthetic intermediate is discussed. Acid catalyzed decomposition of the azide provides the novel product bis(ferrocenylmethyl)amine.
- Bublitz
-
p. 225 - 228
(2008/10/08)
-