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The first example of an efficient and direct dehydrogenative boration of alkenes for vinyl boronate ester synthesis was achieved using a zirconium catalyst. Our methodology avoids using precious transition metals, additional hydrogen acceptors, high temperatures, and long reaction times, which were required to overcome the reducing ability of borane, to give alkyl boronate esters. Detailed mechanistic studies revealed a reversible reaction pathway and further suggested applying the zirconium complex as a ?shuttle catalyst? for transfer boration, which thus sidesteps the use of relatively sensitive borane.

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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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57Fe NMR-spectra of 28 mono and disubstituted ferrocenes with a natural abundance of 57Fe have been measured relative to internal ferrocene.Most of the resonances appear at the high frequency side.The shielding influence of the various substituents is discussed qualitatively. 57Fe shifts are very sensitive to ring tilting as occurring in <3>ferrocenophanes. – Keywords: 57Fe Shifts; Hybridization influence on chemical shifts; Ring tilting

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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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A Cu-catalyzed borylative carboxamidation reaction has been developed using vinylarenes and isocyanates. Alkynes, branched 1,3-dienes, and bicyclic alkenes were also found to be competent coupling partners. Using a chiral phosphanamine ligand, an enantioselective variant of this transformation was developed, affording a set of alpha-chiral amides with unprecedented levels of enantioselectivity. The synthetic utility of the method was demonstrated through a series of representative stereoretentive postcatalytic derivatizations.

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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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Closely spaced 0.2-1 num, Au microelectrodes (50 num long, 1-2 num wide, and 0.1 num thick) on Si3N4 can be functionalized with poly (viniylferrocene), PVFc +/0, or with an N,N’-dibenzyl-4,4′-bipyridinium-based polymer, (BPQ2+/+)n’ derived from hydrolysis of N,N’-bis<(p-trimethoxysilyl)benzyl>-4,4′-bipyridinium (I).Two- or eight-microelectrode arrays have been functionalized with PVFc+/0 or (BPQ2+/+)n.Adjacent microelectrodes can be connected with either polymer in the sense that net current can pass from one microelectrode to another, through the polymer,when one electrode is held at a potential where the polymer is oxidized and the other electrode is held at a potential where the polymer is reduced.From such steady-state current an estimate of the diffusion coefficient for charge transport, DCT, in the polymer can be made; values in the range 10-9 – 10-10 cm2/s are found and accord well with earlier measurements of DCT for the polymers studied.A two-terminal diode can be fabricated by coating one electrode with (BPQ2+/+)n and an adjacent electrode with PVFc+/0 such that there is a connection between the microelectrodes via the (BPQ2+/+)n/PVFc+/0 contact.Current passes when the applied potential is such that the negative lead is attached to the (BPQ2+/+)n-coated electrode and the positive lead is attached to the PVFc+/0-coated electrode.When the applied potential approaches the difference in the Eo’s of the two polymers, current flows with the crucial feature being a downhill (by ca. 0.9 V) cross redox at the (BPQ2+/+)n/PVFc+/0) interface, BPQ+ + Fc+ –> BPQ2+ +Fc0.Current does not flow between the microelectrodes when the applied is in the opposite sense, because the reaction BPQ2+ + Fco –> BPQ+ + Fc+ is uphill by ca. 0.9 V.The switching time of a microelectrochemical diode is controlled by the time required to oxidize and reduce the polymers.

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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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A series of mono- and multimeric polyamine-containing ferrocenyl complexes containing a quinoline motif were prepared. The complexes were characterised by standard techniques. The molecular structure of the monomeric salicylaldimine derivative was elucidated using single crystal X-ray diffraction and was consistent with the proposed structure. The antiplasmodial activity of the compounds were evaluated in vitro against both the NF54 (chloroquine-sensitive) and K1 (chloroquine-resistant) strains of Plasmodium falciparum. The polyamine derivatives exhibit good resistance index values suggesting that these systems are beneficial in overcoming the resistance experienced by chloroquine. Mechanistic studies suggest that haemozoin formation may be the target of these quinoline complexes in the parasite. Some of the complexes exhibit moderate to high cytotoxicity against WHCO1 oesophageal cancer cells in vitro. The monomeric ferrocenyl-amine complexes exhibit potent activity against this particular cell line. The complexes were also screened against the G3 strain of Trichomonas vaginalis and the salicylaldimine complexes demonstrated promising activity at the tested concentration. All of these compounds show no inhibitory effect on several common normal flora bacteria, indicative of their selectivity for eukaryotic pathogens and cancer.

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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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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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A study has been made of the possibility of increasing the stability of the 1,1?-bis(diphenylphosphino)ferrocenium monocation by introduction of appropriate substituents into the cyclopentadienyl ligands. The electrochemical behaviour of a series of 1,1?-bis(diphenylphosphino)ferrocenes bearing substituents with a range of electronic properties has been examined. The results reveal that, the higher the electron-donating ability of the substituents, the longer is the lifetime of the corresponding 1,1?-bis(diphenylphosphino)ferrocenium monocation. However, no stable ferrocenium cation has been obtained; mass spectrometry shows that mixtures of mono- and di-bis(diphenylphosphine)oxides are ultimately formed as products resulting from decomposition of the initially electrogenerated 1,1?-bis(diphenylphosphino)ferrocenium species.

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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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A series of ferrocenyl ended dendrons containing pi-conjugated systems were obtained using Wittig and Heck reactions. The dendrons were attached to eight functionalized resorcinarenes via Williamson reaction obtaining high molecular weight dendrimers. No electronic communication between metal centers was observed by cyclic voltammetry. All the dendrimers were characterized by 1H, 13C NMR, FTIR, UV-Vis, MALDI-TOF, elemental analyses, and electrochemical studies.

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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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Four first- and second-generation heterometallic ferrocenyl derived p-cymene-Ru(II) metallodendrimers, of general formula [DAB-PPI{(kappa6-p-cymene)Ru((C7H5NO)-2-N,O)PTA(5-ferrocenylvinyl)}n][PF6]n and [DAB-PPI{(kappa6-p-cymene)Ru((C6H5N2)-2-N,N)Cl(5-ferrocenylvinyl)}n][PF6]n (where n = 4 (G1), 8 (G2), DAB = 1,4-diaminobutane, PPI = poly(propyleneimine), PTA = 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane) have been synthesized. All complexes have been characterized using analytical (i.e., HR-ESI mass spectrometry, HPLC, elemental analysis, and cyclic voltammetry) and spectroscopic (i.e., 1H and 13C{1H} NMR and infrared) methods. Electrochemical studies reveal that the N,O-p-cymene-Ru(II)-PTA complexes result in two irreversible redox processes (oxidation of the Fe(II) and Ru(II) centers), while the N,N-p-cymene-Ru(II) complexes display one reversible wave (Fe(II)/Fe(III) couple). Heterometallic model complexes have been prepared, and for one of the complexes, its molecular structure has been determined by single-crystal X-ray crystallography. In vitro antiproliferation activity of the dendritic ligands and their complexes were evaluated against A2780 and A2780cisR human ovarian cancer lines, the SISO human cervix cancer line, the LCLC-103H human lung cancer line, and the 5637 human bladder cancer line. Nine of the twelve compounds slowed the growth of the ovarian cancer cell lines by more than 50% at equi-iron concentrations of 5 muM.

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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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Nanoscale lithography of small- and medium-sized molecules on a clean silicon surface was studied using benzene. A scanning tunneling microscopy (STM)-based nanolithographic method was also investigated. The patterning areas of the surface with ethylene and vinyl ferrocene was also discussed. It was observed that any molecules that remain unsaturated after adsorption are candidates to form a monolayer template for this kind of lithography.

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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