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A series of ferrocene derivatives, which have diverse redox potentials modulated by functional groups, have been synthesized as potential ?multi-potential? probes. A Hammett constant analysis revealed a linear free energy correlation between the redox potentials and the electron density of the ferrocene derivatives as determined by the choice of functional group used to modify the ferrocene core.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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We present here the results of a synchrotron radiation-excited UV-photoemission investigation and density functional theory calculations on a structurally related series of organometallic free molecules: ethylferrocene (EtFC), vinylferrocene (VFC), and ethynylferrocene (EFC). This seriesexemplifies the electronic interactions operating when the CC substitue nt group of an aromatic ring is bound to the substrate surface atoms, from a single CC bond to the double and triple CC bond ? systems which are still able to preserve substrate-molecule conjugation. A detailed assignment of the gas phase valence photoelectron spectra is discussed, providing new data on the electronic structure of EtFC and EFC and offering a partial reinterpretation of previous assignments on VFC. The broken symmetry of ferrocene caused by the monosubstitution has notable effectson the removal of the molecular orbital (MO) degeneracy which is found to be especially remarkable for the ferrocenelike e1? MOs. This ef fect is ascribed to the interaction between the aromatic cyclopentadyenyl ring and the substituent through ? hyperconjugation and ? -conjugation mechanisms depending on the nature of the hydrocarbon moiety and its conformational geometry. The vertical ionization energy values of the highest occupied MO for the alkylferrocene and ferrocene free molecules linearly correlate with the redox potential in acetonitrile for ferrocene and the corresponding hybrids obtained by covalently anchoring the free molecule on silicon.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The hydrogen bond directed molecular recognition between 1,1?-bis(ethenyl-4-pyridyl)-ferrocene (1) and (±)-1,1?-binaphthol (2)/(-)-1,1?- binaphthol ((-)-2) has been studied by cocrystallization in different solvents. Single-crystal X-ray structures reveal that 3:2, 2:1, and 1:1 complexes (3, 4, and 5, respectively) of 1,1?-bis(ethenyl-4-pyridyl)ferrocene (1) and (±)-1,1-binaphthol (2) are formed in tetrahydrofuran, methanol, and ethanol, respectively. 5 has a noncentrosymmetric packing arrangement, and an efficiency of 0.3 times that of urea in second-harmonic generation has been measured at 1295 nm. An X-ray crystal structure of 6, 1:1 complex of 1 with (-)-2 in ethanol, reveals that all the molecular dipoles are aligned in the same direction (i.e, a polar crystal), but 6 has modest nonlinear optical properties (ca. 0.4 times that of urea).

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Novel bidentate ligands of general formula (I) are described Formula (I): R represents a hydrocarbyl aromatic structure. The substituent(s) Yx on the aromatic structure has a total X=1-n SigmatYx of atoms other than hydrogen such that x-1-nSigmatYx is ? 4, where n is the total number of substituent(s) Yx and tYx represents the total number of atoms other than hydrogen on a particular substituent Yx. The groups X1, X2, X3 and X4 are joined to Q1 or Q2 via tertiary carbon atoms to the respective atom Q1 or Q2; and Q1 and Q2 each independently represent phosphorus, arsenic or antimony. A catalyst system and a process for the carbonylation of ethylenically unsaturated compounds utilising the catalyst system is also described.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The synthesis and characterization of a novel class of highly-metallized, redox-active polyelectrolytes that employ phosphorus as a scaffold for the installation of transition metals is described. Pyrolysis of thin films of the title polyelectrolytes resulted in the production of magnetite crystallites and ill-defined carbon-, phosphorus- and oxygen-rich phases in char yields of nearly 50%. This journal is the Partner Organisations 2014.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The synthesis of para-substituted ferrocene analogues of stilbene was performed by using the Heck reaction, starting from vinylferrocene. The variation of the electronic density of these compounds with the electronic withdrawing strength of the substituents was studied using 13C NMR spectroscopy, absorption spectra and cyclic voltammetry. The correlation of Hammett constants with the redox properties of the substituted compounds using Nagy’s method allowed us to revisit the determination of the Hammett constants of diethyl phosphonate ester and phosphonic acid substituents. Our measurements were in agreement with the literature except for the diethyl phosphonate group.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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In the present ?genomic era? and in the developing world of DNA chips, DNA detection based on intercalation of specific molecules is of particular interest because the detection process is largely independent of the sequence of the target DNA. In this work, an acridine-orange-based intercalation compound, which was tethered to deglycosylated glucose oxidase was synthesized ad hoc and investigated for its ability to interact with dsDNA. Amperometric detection of DNA hybridization was achieved by signal amplification based on the catalytic oxidation of glucose by DNA-bound glucose oxidase. A clear distinction between dsDNA and ssDNA was achieved by careful design of a DNA-modified electrode surface and prevention of nonspecific adsorption of the acridine-orange-modified enzyme by implementing a potential-assisted immobilization method.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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An improved, short and efficient synthesis of vinylferrocene is reported. This three-step synthesis includes Friedel-Crafts acylation, reduction, and a one-pot mesylation/elimination step to afford the target compound in 62% yield over three steps.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The deprotection of the tert-butyl group of a ferrocenyl uracil Peptide Nucleic Acid (PNA) monomer, Fmoc-aeg(R)-OtBu (1) was achieved using a two step synthesis involving hydrolysis in basic conditions to give first the zwitterion of +NH3-aeg(R)-O- (7). Compound 7 was reacted in situ with N-(9-fluorenylmethoxycarbonyloxy)succinimide to obtain the expected compound Fmoc-aeg(R)-OH (2) (Abbreviations: Aeg = (2-aminoethyl)-glycine; Fmoc = 9-fluorenylmethoxycarbonyl; OtBu = tert-butyl; R = 5-(N-ferroce-nylmethylbenzamido)uracyl). Crown Copyright

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion