cas 1271-47-2, ETHYNYLFERROCENE | Articles data

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Ferrocenylethenylsilatranes and a cymantrenylsilatrane
The syntheses, properties and crystal structures of two isomeric ferrocenylethenylsilatranes and 1-(3-methylcymantrenyl)silatrane are reported. The organometallic moieties and the silatrane show little structural influence on each other. The Si-N distance
Pedersen, Bjorn,Wagner, Gabriele,Herrmann, Rudolf,Scherer, Wolfgang,Meerholz, Klaus,Schmaelzlin, Elmar,Braeuchle, Christoph
p. 129 - 137
(1999)
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Synthesis, Structure, Electrochemical, and Spectroscopic Properties of Hetero-Bimetallic Ru(II)/Fe(II)-Alkynyl Organometallic Complexes
A series of heterobimetallic wire-like organometallic complexes [(tpy-C6H4-R)(PPh3)2Ru-C-C-Fc]+ (tpy-C6H4-R = 4′-(aryl)-2,2′:6′,2′′-terpyridyl, Fc = [(η5-Cp)2Fe], R = -H, -Me, -F, -NMe2 in complexes 5-8, respectively) featuring ferrocenyl and 4′-(aryl)-2,2′:6′,2′′-terpyridyl ruthenium(II) complexes as redox active metal termini, have been synthesized. Various spectroscopic tools, such as multinuclear NMR, IR spectra, HRMS, CHN analyses, and single crystal X-ray crystallography have been utilized to characterize the heterobimetallic complexes. The electrochemical and UV-vis-NIR spectroscopic studies have been investigated to evaluate the electronic delocalization across the molecular backbones of the Ru(II)-Fe(II) heterobinuclear organometallic dyads. Electrochemical studies reveal two well-separated reversible redox waves as a result of successive oxidation of the ferrocenyl and Ru(II) redox centers. The spin density distribution analyses reveal that the initial oxidation process is associated with the Fe(II)/Fe(III) couple followed by one electron oxidation of the ruthenium(II) center. The high Kc value (0.11-1.73 × 1012) and intense NIR absorption, with molar absorption coefficient (in the order of 103 M-1 cm-1) for the RuIIFeIII mixed-valence species, signify strong electronic communication between the two metal termini. The electronic coupling constant (Hab) has been estimated to be 492 and 444 cm-1 for the structurally characterized complexes 6 and 7, respectively. The redox and NIR absorption features indicate that the mixed-valence system of the heterobinuclear dyads belongs to a Robin and Day "class II" system.
Sil, Amit,Ghosh, Utsav,Mishra, Vipin Kumar,Mishra, Sabyashachi,Patra, Sanjib K.
p. 1155 - 1166
(2019)
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Structure, reactivity, and electronic properties of [4]ferrocenophanes and [4]ruthenocenophanes prepared via a novel heteroannular cyclization reaction
The reactions of 1,1′-bis((trimethylsilyl)ethynyl)ferrocene and 1,1′-bis((trimethylsilyl)ethynyl)ruthenocene with catalytic quantities of alkali-metal methoxides in methanol directly afforded the highly unsaturated [4]metallocenophanes 1,1′-d-methoxy-1,3-butadienylene)-ferrocene and 1,1′-(1-methoxy-1,3-butadienylene)ruthenocene, respectively, in high yields via a novel desilylation/heteroannular cyclization sequence. Analogously, 1,1′-bis((trimethylsilyl)ethynyl)octamethylferrocene reacted to give 1,1′-(1-methoxy-1,3-butadienylene)octamethylferrocene in high yield. The reactions of ((trimethylsilyl)ethynyl)ferrocene and ((trimethylsilyl)ethynyl)ruthenocene under identical conditions afforded ethynylferrocene and ethynylruthenocene, respectively. Synthetic elaboration of the heteroannular bridge of the cyclization products provided a route to additional [4]metallocenophanes. Treatment of 1,1′-(1-methoxy-1,3-butadienylene)ferrocene with acidic silica gel afforded 1,1′-(4-oxo-1-butenylene)ferrocene. Reaction of 1,1′-(4-oxo-1-butenylene)ferrocene with alane provided 1,1′-(1-butenylene)ferrocene, while reaction with sodium borohydride gave 1,1′-(4-hydroxy-1-butenylene)ferrocene. Dehydration of 1,1′-(4-hydroxy-1-butenylene)ferrocene on activated alumina provided 1,1′-(1,3-butadienylene)ferrocene. Similar synthetic transformations were carried out to yield the analogous series of ruthenocenophanes and octamethylferrocenophanes. Voltammetric half-wave oxidation potentials were measured for all of the metallocenophanes in order to evaluate the electronic effect of the heteroannular bridges. X-ray crystal structure analyses were carried out on 1-1′-(1-methoxy-1,3-butadienylene)ferrocene and 1,1′-(1-methoxy-1,3-butadienylene)ruthenocene. 1,1′-(1-Methoxy-1,3-butadienylene)ferrocene, C15H14FeO, crystallized in the orthorhombic space group Pcnb with a = 26.997(5) ?, b = 5.981(2) ?, c = 28.962(3) ?, Z = 16, and R = 0.072. 1,1′-(1-Methoxy-1,3-butadienylene)ruthenocene, C15H14RuO, crystallized in the monoclinic C2/c space group with a = 20.590(3) ?, b = 9.023(2) ?, c = 13.940(2) ?, β= 111.296(8)°, Z = 8, and R = 0.021.
Pudelski, John K.,Callstrom, Matthew R.
p. 3095 - 3109
(1994)
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A practical synthesis of ethynylferrocene from ferrocene carboxaldehyde: Structure of 1,4-diferrocenyl-1,3-butadiyne
Ethynylferrocene was satisfactoryly obtained by a Wittig reaction between ferrocene carboxaldehyde and chloromethylentriph-enylphosphonium ylid to give an E/Z mixture of 2-chloro-1-ferrocenylethene. Both isomers were isolated pure by chemical methods. Reaction of the isomers mixture with n-butyllithium allowed ethynylferrocene to be obtained in good yield. The method was applied in one pot giving the ethynylferrocene and (E/Z)-1,4-diferrocenyl-but-1-en-3-yne as a secondary product. Oxidative coupling to 1,4-diferrocenyl-1,3-butadiyne has been carried out in quantitative yields. A single-crystal analysis of the diyne was carried out, but the compound is unreactive in solid state.
Rodriguez, Jose-Gonzalo,Onate, Antonio,Martin-Villamil, Rosa M.,Fonseca, Isabel
p. 71 - 76
(1996)
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New ferrocene-based 2-thio-imidazol-4-ones and their copper complexes. Synthesis and cytotoxicity
Synthesis, characterization (HRMS, NMR, EPR, XANES, UV-Vis spectroscopy, and electrochemistry), DNA and BSA binding and in vitro biological screening of two new ferrocene-incorporated thiohydantoin derivatives (5 and 6) and their copper coordination compounds are reported. The ferrocene-based thiohydantoin derivatives were prepared by copper-catalyzed azide alkyne cycloaddition reactions between alkynyl ferrocenes and 5-(Z)-3-(2-azidoethyl)-2-(methylthio)-5-(pyridin-2-ylmethylene)-1H-imidazol-4H-one. Alkynyl ferrocenes necessary for these syntheses were prepared by new procedures. Intermolecular redox reactions between the ferrocene fragment and copper(+2) coordinated ions were studied by different methods to determine the mechanism and kinetic constants of redox processes. Ferrocene-containing imidazolones (5 and 6) and their copper complexes were also tested for their in vitro cytotoxic activity against MCF-7 and A-549 carcinoma cells, and also against the noncancerous cell line Hek-293. The results showed modest cytotoxicity against the subjected cancer cell line compared with cisplatin. The ability of the obtained compounds to cause DNA degradation and cell apoptosis was investigated, and the distribution of cytosol/pellets was studied by AAS.
Guk,Krasnovskaya,Dashkova,Skvortsov,Rubtsova,Dyadchenko,Yudina,Kosarev,Soldatov,Shapovalov,Semkina,Vlasova,Pergushov,Shafikov,Andreeva,Melnikov,Zyk,Majouga,Beloglazkina
p. 17357 - 17366
(2018)
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Synthesis and some reactions of ferrocenylacetylenes
The conversion of acetylferrocene or diacetylferrocene into ethynylferrocene 1 or diethynylferrocene 4, respectively, is achieved in good yield in a one-pot synthesis using Negishi's reagent.The diethynylferrocene is isolated as its trimethylsilylderivative 5.The complexes 1 and 5 undergo various nucleophilic substitution reactions, resulting in new ferrocenyl derivatives.
Doisneau, G.,Balavoine, G.,Fillebeen-Khan, T.
p. 113 - 117
(1992)
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Synthesis of a diferrocenylvinylidene complex by migration of a ferrocenyl substituent
An unusual 1,2-ferrocenyl migration has been observed following reactions of [Ru(dppe)Cp][BArF4] with diferrocenylacetylene, extending the scope of group rearrangments beyond methyl (Wagner-Meerwein) and phenyl entities. Ferrocene-containing bis(alkynes) RCCArCCR (R = Fc, Ar = 1,4-phenylene; R = Ph, Ar = 1,1′-ferrocenylene) gave bimetallic bis(vinylidene) complexes following two consecutive rearrangements.
Korb, Marcus,Moggach, Stephen A.,Low, Paul J.
supporting information
p. 4251 - 4254
(2021/05/05)

METAL-ORGANIC POLYHEDRAL INCLUDING METALLOCENE STRUCTURE AND METHOD FOR PREPARING THE SAME
Disclosed are a metal-organic polyhedron including a metallocene structure and a method for manufacturing the same. Since the metal-organic polyhedron including the metallocene structure has high porosity and excellent electrical conductivity, when metal-organic polyhedron is used for electrodes such as supercapacitors or secondary batteries and the like, energy density and output characteristics of a device can be improved.
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(2021/06/22)

Novel ferrocene-labeled propargyl amines via CuI multicomponent amination/alkynylation
An efficient synthesis of ferrocene-tagged propargyl amine derivatives via one-pot three-component domino amination/alkynylation in water is reported. The synthesis involves a single Cu(i) catalyst without addition of a ligand, has broad substrate applicability and gives excellent yields.
Srivastava, Suman
supporting information
p. 6469 - 6471
(2019/05/04)

Synthesis and Characterization of Diferrocenyl Conjugates: Varying π-Conjugated Bridging Ligands and its Consequence on Electrochemical Communication
Organometallic wire-like complexes with ferrocenyl termini, conjugated with one and two units of thienylethynyl (M1 and M2) and thienyl (M3 and M4) groups, have been synthesized with a general formula of [Fc-C≡C-(Th-C≡C)1-2-Fc] and [Fc-(Th)1-2-Fc] (Fc = ferrocenyl, Th = thienyl) respectively. The diferrocenyl organometallic complexes have been characterized by various spectroscopic tools such as multinuclear NMR, FTIR, elemental analysis, and mass spectrometry. The electrochemical properties of these compounds have been investigated by cyclic (CV) and differential pulse voltammetry (DPV). The single reversible oxidation wave in diferrocenyl complexes with thienylethynyl spacers (M1 and M2) indicates the absence of intramolecular electrochemical communication between the two ferrocenyl termini. Interestingly, the diferrocenyl complexes with one and two thienyl spacers (M3 and M4) show two successive reversible one-electron oxidation waves, indicating electronic coupling between the two ferrocenyl (Fc) termini. The potential difference (ΔE1/2) between the two redox centers is 160 mV and 130 mV, respectively, with the corresponding comproportionation constants (Kc) of 6.2 × 102 and 1.5 × 102. Upon mono-oxidation of M3 by [Cp2Fe][BF4], a broad and weak intervalence charge-transfer (IVCT) transition is observed in the NIR region of 1200–2200 nm.
Roy, Sourav Saha,Patra, Sanjib K.
supporting information
p. 2193 - 2201
(2019/04/17)

DBU-Mediated Synthesis of Aryl Acetylenes or 1-Bromoethynylarenes from Aldehydes
Two well known synthetic organic reactions Ramirez olefination and Corey-fuchs reactions are integrated in one-pot sequential manner for the synthesis of arylacetylenes and 1,3-enynes starting directly from commercially available aldehydes. The bicyclic amidine 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) along with additive NaOH not only exclusively afforded the terminal alkynes directly from the aldehydes, but also enhanced the reaction rate. The dynamic nature of DBU also facilitated the isolation of 1-bromoalkynes intermediate products. Selection of additive from NaOH and H2O served as a switch for the synthesis of terminal alkyne and 1-bromoalkynes, respectively. (Figure presented.).
Thummala, Yadagiri,Karunakar, Galla V.,Doddi, Venkata Ramana
supporting information
p. 611 - 616
(2019/01/04)

Design, synthesis and fungicidal activity studies of 3-ferrocenyl-N-acryloylmorpholine
Ferrocene and its derivatives have been widely used in many fields and also used to modify and improve the performance. Particularly, their low toxicity also attract much attention in medical and pesticide fields. In order to get fungicides with higher biological activity, ferrocenyl groups were introduced into the skeleton of dimethomorph instead of phenyl groups and a series of 3-ferrocenyl-N-acryloylmorpholine were synthesized. The fungicidal bioassay results indicated that most of compounds showed moderate fungicidal activities against 14 kinds of agricultural pathogenic fungi and some compounds displayed higher fungicidal activities than that of dimethomorph. Intrestlingly, compounds 5(Z) exhibited better fungicidal activity against Sclerotinia sclerotiorum than that of compound 5(E).
Chen, Peiqi,Liu, Chunjuan,Hu, Jianfeng,Zhang, Hao,Sun, Ranfeng
p. 113 - 121
(2017/12/12)

Synthesis of tetracyanoethylene-substituted ferrocene and its device properties
Small organic molecules are promising candidates for cheaper, flexible and good-performance sources for organic solar cells (OSCs) due to their easy fabrication, low cost and slightly cheaper processing. However, the lower power conversion efficiency of OSCs is the main problem for their applications. Ferrocene structures could be the best candidates for the active layers of OSCs due to their unique properties such as thermal and chemical stability. The electrochemical, electro-optical and solar cell performances of 2,5-dicyano-3-ferrocenyl-4-ferrocenylethynylhexa-2,4-dienedinitrile (DiCN-Fc) structures were investigated. First, the electrochemical and electro-optical properties were examined for finding the highest occupied and lowest unoccupied molecular orbital values and bandgap of DiCN-Fc. The best photovoltaic performance was obtained with 7?wt% of DiCN-Fc loading, with a power conversion efficiency of about 4.27%. In the light of our investigations, ferrocenyl-substituted small organic molecules could contribute to the development of organic photovoltaic devices.
Kivrak, Arif,Zobi, Cengiz,Torlak, Yasemin,?aml?soy, Ye?im,Ku?, Mahmut,Kivrak, Hilal
(2018/08/03)

The synthesis, structural characterization and biological evaluation of novel N-{para-(ferrocenyl) ethynyl benzoyl} amino acid and dipeptide methyl and ethyl esters as anticancer agents
A series of N-{para-(ferrocenyl) ethynyl benzoyl} amino acid and dipeptide methyl and ethyl esters 4–18 were prepared by coupling para-(ferrocenyl) ethynyl benzoic acid 3 to the amino acids GABA(OMe), GABA(OEt) and the dipeptide esters GlyGly(OMe), GlyGly(OEt), Gly-L-Ala(OMe), Gly-L-Ala(OEt), Gly-D-Ala(OMe), Gly-D-Ala(OEt), Gly-L-Leu(OEt), Gly-L-Phe(OEt), SarGly(OMe), SarGly(OEt), Sar-L-Ala(OEt), L-ProGly(OEt) and L-Pro-L-Ala(OEt) using the standard N-(3-dimethylaminopropyl)-N’-ethylcarbodiimide hydrochloride (EDC), 1-hydroxybenzotriazole (HOBt) protocol. All the compounds were fully characterized using a combination of I.R., UV-Vis, 1H NMR, 13C NMR, DEPT-135, 1H-13C COSY (HMQC) spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Selected compounds 5, 7, 9, 11, 16, 17 and 18 showed micromolar activity in the H1299 NSCLC cell line, with IC50 values in the range of 3.8–8.3 μM.
Harry, Andy G.,Murphy, James P.,O'Donovan, Norma,Crown, John,Rai, Dilip K.,Kenny, Peter T.M.
p. 379 - 388
(2017/07/25)

Colchicine metallocenyl bioconjugates showing high antiproliferative activities against cancer cell lines
A series of ferrocenyl and ruthenocenyl conjugates with colchicine bearing a 1,2,3-triazole moiety were synthesized and their anticancer properties were evaluated. We found that the most potent metallocenyl derivatives Rc4 and Rc5 are 6-7 times more cytotoxic toward HepG2 cells, while Fc4 and Fc5 are two times more cytotoxic toward HCT116 cells as colchicine. We also found that compounds Fc4, Fc5, Rc1 and Rc3-Rc5 are able to induce apoptosis, while compound Fc2 arrests mitosis.
Kowalczyk, Karolina,B?auz, Andrzej,Ciszewski, Wojciech M.,Wieczorek, Anna,Rychlik, B?azej,Plazuk, Damian
p. 17041 - 17052
(2017/12/26)

Preparation of Bodipy-ferrocene dyads and modulation of the singlet/triplet excited state of bodipy: Via electron transfer and triplet energy transfer
Modulation of the singlet/triplet excited state of a fluorophore is becoming more important for molecular switches, molecular memory devices, chemical or biological sensors and controllable photodynamic therapy (PDT) etc. Boron-dipyrromethene (Bodipy)-ferrocene (Fc) dyads were prepared for reversible electrochemical switching of the singlet excited state (fluorescence), as well as the triplet excited states of Bodipy. The photophysical properties of the dyads were studied using steady-state UV-vis absorption spectroscopy, fluorescence, electrochemical characterization, time-resolved fluorescence and nanosecond transient absorption spectroscopies. The fluorescence of the Bodipy moieties in the dyads was quenched significantly, due to the photo-induced electron transfer (PET). This conclusion was supported by electrochemical characterization and calculation of the Gibbs free energy changes of PET. We demonstrated that the fluorescence of the Bodipy moiety can be reversibly switched ON and OFF by electrochemical oxidation of the Fc moiety (Fc/Fc+). Furthermore, we proved that the Fc moiety is efficient for quenching of the triplet excited states of Bodipy. Two quenching mechanisms, PET and triplet-triplet-energy transfer (TTET), are responsible for the intramolecular and intermolecular quenching of the triplet excited states of the diiodoBodipy unit.
Wu, Xueyan,Wu, Wenting,Cui, Xiaoneng,Zhao, Jianzhang,Wu, Mingbo
supporting information
p. 2843 - 2853
(2016/04/26)

The Dual Role of 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) in the Synthesis of Terminal Aryl- and Styryl-Acetylenes via Umpolung Reactivity
The dual role of the bicyclic amidine base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was demonstrated in a synthesis of terminal aryl- and styryl-acetylenes. Mechanistically, a tandem process involving elimination/Umpolung/protonation occurs in a single step to generate terminal aryl- and styryl-acetylenes from geminal dibromoalkenes. The key to the success of this transformation lies in the organobase-mediated generation of the acetylide from the 1-bromoalkynes at room temperature. The unique characteristics of DBU as an inherently safer reagent make it an attractive alternative to previous systems wherein required pyrophoric reagents and nonambient temperatures remain unsolved issues. The procedure does not work for the synthesis of alkyl-acetylenes.
Morri, Ashok Kumar,Thummala, Yadagiri,Doddi, Venkata Ramana
supporting information
p. 4640 - 4643
(2015/09/28)

Synthesis, linear and nonlinear optical properties of thermally stable ferrocene-diketopyrrolopyrrole dyads
A set of new ferrocene-diketopyrrolopyrrole (Fc-DPP) conjugated dyads was synthesized and their optical, nonlinear optical (NLO) and electrochemical properties were investigated. The second-order nonlinear polarizabilities were determined using hyper-Rayleigh scattering with femtosecond pulsed laser light at 840 nm. The dyads exhibited structure dependent NLO response, which could be explained by correlating optical as well as electrochemical data. In the latter case, it is shown that the amplitude of the Fc based one-electron redox process of D-π-A type dyads is doubled in the dyads of the type D-π-A-π-D, where the acceptor (DPP) is flanked by two Fc donors.
Kaur, Sarbjeet,Dhoun, Sugandha,Depotter, Griet,Kaur, Paramjit,Clays, Koen,Singh, Kamaljit
p. 84643 - 84656
(2015/10/28)

Phosphinoferrocene ureas: Synthesis, structural characterization, and catalytic use in palladium-catalyzed cyanation of aryl bromides
Phosphinoferrocene ureas Ph2PfcCH2NHCONR2, where NR2 = NH2 (1a), NHMe (1b), NMe2 (1c), NHCy (1d), and NHPh (1e); the analogous thiourea Ph2PfcCH2NHCSNHPh (1f); and the acetamido derivative Ph2PfcCH2NHCOMe (1g) (Cy = cyclohexyl, fc = ferrocene-1,1′-diyl) were prepared via three different approaches starting from Ph2PfcCH2NH2·HCl (3·HCl) or Ph2PfcCHO (4). The reactions of the representative ligand 1e with [PdCl2(cod)] (cod = cycloocta-1,5-diene) afforded [PdCl(μ-Cl)(1e-κP)2]2 or [PdCl2(1e-κP)2]2 depending on the metal-to-ligand stoichiometry, whereas those with [PdCl(η3-C3H5)]2 and [PdCl(LNC)]2 produced the respective bridge cleavage products, [PdCl(η3-C3H5)(1e-κP)] and [PdCl(LNC)(1e-κP)] (LNC = [(2-dimethylamino-κN)methyl]phenyl-κC1). Attempts to involve the polar pendant in coordination to the Pd(II) center were unsuccessful, indicating that the phosphinoferrocene ureas 1 bind Pd(II) preferentially as modified phosphines rather than bifunctional donors. When combined with palladium(II) acetate, the ligands give rise to active catalysts for Pd-catalyzed cyanation of aryl bromides with potassium hexacyanoferrate(II). Optimization experiments revealed that the best results are obtained in 50% aqueous dioxane with a catalyst generated from 1 mol % of palladium(II) acetate and 2 mol % of 1e in the presence of 1 equiv of Na2CO3 as the base and half molar equivalent of K4[Fe(CN)6]·3H2O. Under such optimized conditions, bromobenzenes bearing electron-donating substituents are cyanated cleanly and rapidly, affording the nitriles in very good to excellent yields. In the case of substrates bearing electron-withdrawing groups, however, the cyanation is complicated by the hydrolysis of the formed nitriles to the respective amides, which reduces the yield of the desired primary product. Amine- and nitro-substituted substrates are cyanated only to a negligible extent, the former due to their metal-scavenging ability.
?koch, Karel,Císa?ová, Ivana,?těpni?ka, Petr
p. 1942 - 1956
(2015/06/08)

Synthesis and antiviral evaluation of 4′-(1,2,3-triazol-1-yl) thymidines
Non-obligate chain terminating nucleosides with a linear substituent (azido or ethynyl group) at the 4′ position represent an important class of compounds in antiviral discovery, particularly against hepatitis C virus (HCV) and human immunodeficiency virus (HIV). We have previously shown that 3′-azidothymidine (AZT)-derived 1,2,3-triazoles can be potent inhibitors of HIV-1. To gauge the medicinal chemistry impact of functionalizing the 4′-linear substituent and possibly generate novel antiviral nucleoside scaffolds, we have explored azide-alkyne cycloaddition reactions with 4′-azidothymidine (ADRT). The Ru-mediated reaction failed and the Cu-catalyzed variant generated 1,2,3-triazoles (9a-y) with only modest yields and efficiencies, indicating a substantial steric barrier around the 4′-azido group. Antiviral screening identified a few triazole analogues moderately active against HIV-1 (18-62% inhibition at 10 μM) and/or influenza A virus (15-50% inhibition at 10 μM), and none active against West Nile virus (WNV) or HCV. These results suggest that the linear 4′ azido group of ADRT may be essential for target binding and that its chemical manipulation could largely compromise antiviral potency. This journal is the Partner Organisations 2014.
Vernekar, Sanjeev Kumar V.,Qiu, Li,Zacharias, Jeana,Geraghty, Robert J.,Wang, Zhengqiang
supporting information
p. 603 - 608
(2014/05/06)

Gold-catalyzed oxazoles synthesis and their relevant antiproliferative activities
Nine 5-aryl-2-methyloxazole derivatives were synthesized via gold-catalyzed alkyne oxidation. All of the compounds have been screened for their antiproliferative activities against MCF-7 cell (human breast carcinoma), A549 cell (human lung carcinoma) and
Wu, Chao,Liang, Zhi-Wu,Xu, Ying-Ying,He, Wei-Min,Xiang, Jian-Nan
p. 1064 - 1066
(2014/01/06)

Long-range intramolecular electronic communication in bis(ferrocenylethynyl) complexes incorporating conjugated heterocyclic spacers: Synthesis, crystallography, and electrochemistry
A new series of bis(ferrocenylethynyl) complexes, 3-7, and a mono(ferrocenylethynyl) complex, 8, have been synthesized incorporating conjugated heterocyclic spacer groups, with the ethynyl group facilitating an effective long-range intramolecular interaction. The complexes were characterized by NMR, IR, and UV-vis spectroscopy as well as X-ray crystallography. The redox properties of these complexes were investigated using cyclic voltammetry and spectroelectrochemistry. Although there is a large separation of ～14 A between the two redox centers, ΔE 1/2 values in this series of complexes ranged from 50 to 110 mV. The appearance of intervalance charge-transfer bands in the UV-vis-near-IR region for the monocationic complexes further confirmed effective intramolecular electronic communication. Computational studies are presented that show the degree of delocalization across the Fc-C≡C-C≡C-Fc (Fc = C 5H5FeC5H4) highest occupied molecular orbital.
Shah, Hakikulla H.,Al-Balushi, Rayya A.,Al-Suti, Mohammed K.,Khan, Muhammad S.,Woodall, Christopher H.,Molloy, Kieran C.,Raithby, Paul R.,Robinson, Thomas P.,Dale, Sara E. C.,Marken, Frank
p. 4898 - 4908
(2013/06/05)

The preparation, spectroscopy, structure and electrochemistry of some [Co(η4-C4Ph4)(η5-C 5H4CC-CHY)], [Fe(η5-C5H 5)(η5-C5H4CC-CHY)], and related complexes
[Co(η4-C4Ph4)(η5-C 5H4CC-CHO)], 4a, has been prepared from [Co(η4-C4Ph4)(η5-C 5H4CHO)], 1a, by reactions similar to those used previously to convert [Fe(η5-C5H5) (η5-C5H4CHO)], 1b, to [Fe(η 5-C5H5)(η5-C5H 4CC-CHO)], 4b, i.e. via the dibromoethene [Co(η4- C4Ph4)(η5-C5H 4CHCBr2)], 2a, and alkyne [Co(η4-C 4Ph4)(η5-C5H4CCH)], 3a. Both 4a and 4b undergo the normal aldehyde reactions with malononitrile and 2,4-dinitrophenylhydrazines to give their respective condensation products [Co(η4-C4Ph4){η5-C 5H4CC-CHC(CN)2}], 5a, and [Fe(η 5-C5H5){η5-C5H 4CC-CHC(CN)2}], 5b; [Co(η4-C 4Ph4){η5-C5H4CC-CHN- N(H)C6H3(NO2)2-2,4}], 6a, and [Fe(η5-C5H5){η5-C 5H4CC-CHN-N(H)C6H3(NO 2)2-2,4}], 6b, as separable mixtures of syn- and anti-isomers; and the anti-isomers of [Co(η4-C4Ph 4){η5-C5H4CC-CHN-N(Me)C 6H3(NO2)2-2,4}], 7a, and [Fe(η5-C5H5){η5-C 5H4CC-CHN-N(Me)C6H3(NO 2)2-2,4}], 7b. With [Fe2(η-C 5H5)2(CO)2(μ-CO)(μ-CMe)] [BF4] 4a and 4b form blue-green [Fe2(η-C 5H5)2(CO)2(μ-CO)(μ-C-CHCH-CC- C5H4-η5)Co(η4-C 4Ph4)][BF4], [8a][BF4], and black [Fe2(η-C5H5)2(CO) 2(μ-CO)(μ-C-CHCH-CC-C5H4- η5)Fe(η5-C5H5)][BF 4], [8b][BF4] salts. 4a and 4b also react with the Wittig reagent [Fe(η5-C5H5)(η5- C5H4-CH2PPh3)][I]/nBuLi to give mixtures of Z and E-[Co(η4-C4Ph 4)(η5-C5H4-CC-CHCH-C 5H4-η5)Fe(η5-C 5H5)], 9a, and [Fe(η5-C5H 5)(η5-C5H4-CC-CHCH-C 5H4-η5)Fe(η5-C 5H5)], 9b, which are separable for 9b but not 9a. The Wittig reagent obtained from [Co(η4-C4Ph 4)(η5-C5H4-CH 2PPh3)][Cl]/nBuLi failed to react with 4a or 4b, but the reaction of 4a with [ClCH2PPh3][Cl]/ tBuOK gives very low yields of one expected product, E-[Co(η4-C4Ph4)(η5-C 5H4-CC-CHCH-C5H4-η5) Co(η4-C4Ph4)], E-10a, together with a number of other unidentified compounds. The IR, 1H NMR and 13C NMR, and UV/Vis spectra of 4-9 are reported, assigned and discussed. They confirm that 4-9 are Donor-π-Acceptor complexes in which Co(η4-C4Ph4)(η5-C 5H4-) is a weaker donor than Fe(η5-C 5H5)(η5-C5H4-), the acceptor strength increases for Acceptor CHCHFc 6H 3(NO2)2-2,4 2 μ+)(μ-CO)(CO)2Fe 2(η5-C5H5)2, and that an ethyne linker, π = CC, is less effective than an ethene linker, π = CHCH, in promoting electronic communication between the Donor and Acceptor. The molecular structures of 2a, 3a, 4a, 4b, 5b, syn-6a, syn-6b (two crystal forms) and anti-7b have been determined by X-ray diffraction. They have normal molecular dimensions, and the C5H4-CC-CHY moiety does not deviate greatly from planarity with angles between the C5H 4 and C-C(H)Y planes of 4.2-19.6°. This contrasts with the structures of Fc-CC-R (R = aryl) complexes where the C5H4 and aryl planes are orthogonal or close to it. The electrochemistry of 3a/3b, 4a/4b, 5a/5b, syn-6a/6b, anti-7a/7b, E/Z-9a, Z-9b, E-9b and [Co(η 4-C4Ph4)(η5-C5H 4-CC-C6H5)] has been studied. The Co(η4-C4Ph4)(η5-C 5H4-) complexes undergo reversible 1e oxidations at higher E° than their Fe(η5-C5H5) (η5-C5H4-) counterparts with E° increasing as the electron-withdrawing ability of the acceptor group increases. Furthermore, like their ferrocenyl counterparts, the alkyne derivatives [Co(η4-C4Ph4)(η5-C 5H4-CC-X)] are oxidised at a more positive E° than the alkene complexes [Co(η4-C4Ph4) (η5-C5H4-CHCH-X)]. The UV/Visible spectrum of the oxidized species [Co(η4-C4Ph 4)(η5-C5H4-CC-C 6H5)]+ shows an absorption band at 960 nm due to a C6H5 → Co(η4-C4Ph 4)(η5-C5H4-) charge transfer transition; its equivalent in the spectrum of [Fe(η5-C 5H5)(η5-C5H4-CC- C6H5)]+ is found at 797 nm. This implies that {Co(η4-C4Ph4)(η5-C 5H4-)}+ is a stronger acceptor than {Fe(η5-C5H5)(η5-C 5H4-)}+.
Courtney, Donagh,John McAdam,Manning, Anthony R.,Müller-Bunz, Helge,Ortin, Yannick,Simpson, Jim
p. 7 - 22
(2012/04/17)

Cationic (η6-Arene)tricarbonylmanganese Linked to Ferrocene Complexes
Palladium-catalyzed Sonogashira coupling reactions of the neutral [η 5(1-5)-(1-chloro-4-methoxycyclohexa-2,4-dienyl)] tricarbonylmanganese(I) (2) and 2-bromo-5-{[η 5(1-5)-(4-methoxycyclohexa-2,4-dienyl]tricarbonylmanganese(I)} thioph
Jacques, Beatrice,Tranchier, Jean-Philippe,Rose-Munch, Francoise,Rose, Eric,Stephenson, G. Richard,Guyard-Duhayon, Carine
p. 184 - 193
(2008/10/09)

Conversion of methyl ketones into terminal acetylenes: Ethynylferrocene: [Ferrocene, ethynyl]
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Polin, Johann,Schottenberger, Herwig,Anderson, Bruce,Martin, Stephen F.
p. 262 - 262
(2017/09/23)