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The anodic electrochemical oxidations of ReCp(CO)3 (1, Cp = eta5-C5H5), Re(eta5-C 5H4NH2)(CO)3 (2), and ReCp*(CO)3 (3, Cp* = eta5-C 5Me5), have been studied in CH2Cl2 containing [NBu4][TFAB] (TFAB = [B(C6F5) 4]-) as supporting electrolyte. One-electron oxidations were observed with E1/2 = 1.16, 0.79, and 0.91 V vs ferrocene for 1-3, respectively. In each case, rapid dimerization of the radical cation gave the dimer dication, [Re2Cpgamma2(CO) 6]2+ (where Cpgamma represents a generic cyclopentadienyl ligand), which may be itself reduced cathodically back to the original 18-electron neutral complex ReCpgamma(CO)3. DFT calculations show that the SOMO of 1+ is highly Re-based and hybridized to point away from the metal, thereby facilitating the dimerization process and other reactions of the Re(II) center. The dimers, isolated in all three cases, have long metal-metal bonds that are unsupported by bridging ligands, the bond lengths being calculated as 3.229 A for [Re 2Cp2(CO)6]2+ (12 2+) and measured as 3.1097 A for [Re2(C 5H4NH2)2(CO)6] 2+ (222+) by X-ray crystallography on [Re 2(C5H4NH2)2(CO) 6][TFAB]2. The monomer/dimer equilibrium constants are between Kdim = 105 M-1 and 107 M-1 for these systems, so that partial dissociation of the dimers gives a modest amount of the corresponding monomer that is free to undergo radical cation reactions. The radical 1+ slowly abstracts a chlorine atom from dichloromethane to give the 18-electron complex [ReCp(CO) 3Cl]+ as a side product. The radical cation 1+ acts as a powerful one-electron oxidant capable of effectively driving outer-sphere electron-transfer reactions with reagents having potentials of up to 0.9 V vs ferrocene.

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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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In (1?-benzoylferrocenyl)diphenylmethanol, [(PhCO-C5H4)Fe(C5H4)]CPh 2OH (C30H24FeO2), there is an intramolecular O-H…O hydrogen bond with O…O 2.891 (2) A; the ferrocenyl unit adopts an eclipsed conformation and the molecules are linked into centrosymmetric dimers by C-H…O hydrogen bonds with C…O 3.357 (3) A, to generate a cyclic R44(16) motif.

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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 diffusion of sugar in aqueous solution is important both in nature and in technological applications, yet measurements of diffusion coefficients at low water content are scarce. We report directly measured sucrose diffusion coefficients in aqueous solution. Our technique utilises a Raman isotope tracer method to monitor the diffusion of non-deuterated and deuterated sucrose across a boundary between the two aqueous solutions. At a water activity of 0.4 (equivalent to 90 wt% sucrose) at room temperature, the diffusion coefficient of sucrose was determined to be approximately four orders of magnitude smaller than that of water in the same material. Using literature viscosity data, we show that, although inappropriate for the prediction of water diffusion, the Stokes-Einstein equation works well for predicting sucrose diffusion under the conditions studied. As well as providing information of importance to the fundamental understanding of diffusion in binary solutions, these data have technological, pharmaceutical and medical implications, for example in cryopreservation. Moreover, in the atmosphere, slow organic diffusion may have important implications for aerosol growth, chemistry and evaporation, where processes may be limited by the inability of a molecule to diffuse between the bulk and the surface of a particle.

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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 potassium bis-dithiocarbamate (bis-dtc) salts of 1,3- bis(benzylaminomethyl)benzene (1,3-Bn-ambdtc), 1,3-bis(iso-butylaminomethyl) benzene (1,3-iBu-ambdtc), 1,4-bis(benzylaminomethyl)benzene (1,4-Bn-ambdtc), and 1,4-bis(iso-butylaminomethyl)benzene (1,4- iBu-ambdtc) were reacted with three different diorganotin dichlorides (R2SnCl2 with R = Me, nBu, and Ph) in 1:1 stoichiometric ratios to give the corresponding diorganotin bis- dithiocarbamates. Additionally, the dimethyltin bis-dithiocarbamate of 1,1?-bis(benzylaminomethyl)ferrocene (1,1?-Bn-amfdtc) was prepared. The resulting complexes have been characterized as far as possible by elemental analysis, FAB+ mass spectrometry, IR and NMR (1H, 13C, and 119Sn) spectroscopy, and single-crystal X-ray diffraction, showing that the tin complexes are dinuclear 24- and 26-membered macrocyclic species of composition [{R2Sn(bis-dtc)}2]. As shown by 119Sn NMR spectroscopy, the tin centers are hexa-coordinated in all cases; however, two different coordination environments are possible, as detected by single-crystal X-ray diffraction. In the dimethyltin derivatives of 1,3-Bn-ambdtc, 1,3-iBu-ambdtc, 1,4-Bn-ambdtc, and 1,1?-Bn-amfdtc and the di-n-butyltin derivative of 1,3- iBu-ambdtc, the metal atoms are embedded in skewed-trapezoidal- bipyramidal coordination polyhedra with asymmetrically coordinating trans-oriented dtc groups. In contrast, in the diphenyltin derivative 1,3- iBu-ambdtc, the metal centers have distorted octahedral coordination with symmetrically coordinating cis-oriented dtc functions. Thus, for the complexes derived from 1,3-Bn/iBu-ambdtc, two different macrocyclic structures were observed. In the dimethyl- and di-n-butyltin derivatives, the bridging bis-dtc ligands adopt U-shaped conformations, while in the case of the diphenyltin derivative, the conformation is L-shaped. Furthermore, two different macrocyclic ring conformations can occurr, which differ in the spatial orientation of the substituents attached to the nitrogen atoms (Bn or iBu). The dimethyltin derivatives of 1,4-Bn-ambdtc and 1,1?-Bn-amfdtc have cavities, in which aromatic rings are accomodated in the solid state.

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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 reactions of mono(cyclopentadienyl)titanium(IV) trichloride with a new class of Schiff bases (H2L), derived by condensing 1,1?-diacetylferrocene with different 3-substituted phenyl-4-amino-5- mercapto-1,2,4-triazoIes, have been studied both by a conventional stirring method and also using microwave technology. Binuclear products of type [{eta5-C5H5)TiCl2}2 (L)] have been isolated in both cases. Tentative structural conclusions are drawn for the reaction products based upon analysis, electrical conductance, magnetic moment and spectral (UV-Visible, IR, 1H NMR and 13C NMR) data. FAB mass spectra of complexes were also recorded to confirm the binuclear structures. Studies were conducted to assess the growth inhibiting potential of the ligands and complexes against various fungal and bacterial strains.

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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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Electrodeposition of Sn from supercritical difluoromethane has been performed into anodic alumina templates with pores down to 3 nm in diameter and into mesoporous silica templates with pores of diameter 1.5 nm. Optimized deposits have been characterized using X-ray diffraction, scanning electron microscopy, and scanning transmission electron microscopy (bright field, high-angle annular dark field, and energy-dispersive X-ray elemental mapping). Crystalline 13 nm diameter Sn nanowires have been electrodeposited in symmetric pore anodic alumina. Direct transmission electron microscopy evidence of sub 7 nm Sn nanowires in asymmetric anodic alumina has been obtained. These same measurements present indirect evidence for electrodeposition through 3 nm constrictions in the same templates. A detailed transmission electron microscopy study of mesoporous silica films after Sn deposition is presented. These indicate that it is possible to deposit Sn through the 1.5 nm pores in the mesoporous films, but that the nanowires formed are not stable. Suggestions of why this is the case and how such extreme nanowires could be stabilized are presented.

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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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A scanning electrochemical microscope (SECM) in the feedback and generation-collection modes was used to investigate the regeneration of photoexcited dye cations at the semiconductor/electrolyte interface in a dye-sensitized solar cell (DSSC) based on ZnO/D149. An effective dye regeneration rate constant kox of 9.55 × 107 cm 9/2 mol-3/2 s-1 was obtained from feedback mode experiments at different wavelengths and light intensities on ZnO/D149 electrodes. Illuminated regions of the dye-sensitized electrodes could be differentiated from non-illuminated regions by local imaging in SECM generation-collection experiments with I- as redox mediator. We also report SECM feedback measurements on non-illuminated dye-sensitized electrodes to investigate the electron transfer kinetics of dissolved redox couples at the underlying FTO substrate.

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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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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 muM against MCF-7 and 79.63 muM 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 alpha and beta.

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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 thiophene tungsten Fischer carbene complexes of type [(CO)5W=C(OMe)R] (1, R = 2-Th; 4, R = fcthFc) and [(CO)5W=C(OMe)-R?-(OMe)C=W(CO)5] (2, R? = th; 5, R? = fcthfc) was synthesized for investigating low energy charge transfer interactions between the carbene substituents and the transition metal carbonyl fragment incorporating the thiophene heterocyclic system (Th = Thienyl; th = 2,5-thiendiyl; Fc = ferrocenyl; fc = 1,1?-ferrocenediyl). Electrochemical investigations were carried out on these complexes to get a closer insight into the electronic properties of 1, 2, 4 and 5. Typical electrode reactions could be found for the carbene reductions itself and for the tungsten carbonyl oxidation processes in all metal carbene complexes. However, for the thiophene complex 2 two well-separated one-electron reduction events were observed, suggesting an interaction of the Fischer carbene moieties in 2-, over the thiophene bridge. Reversible one-electron redox events for the ferrocenyl moieties in complexes 4 and 5 were also observed. During the UV-Vis-NIR spectroelectrochemical investigations typical low energy absorptions for the mixed-valent alpha,alpha?-diferrocenyl thiophene increment were found for these two complexes, as well as high energy NIR absorptions, which were attributed to metal-metal charge transfer transition between the tungsten carbonyl increment and the ferrocenyl units (complexes 4 and 5). Further infrared spectroelectrochemical studies reveal that the electronic interactions between the tungsten carbene and the ferrocenyl electrophores in the corresponding cationic species (4+, 42+, 5+, 52+) can be described with weakly coupled class II systems according to Robin and Day.

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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 base-free nickel-catalyzed hydroboration of unreactive simple alkenes with bis(pinacolato)diboron using methanol as the hydride source under mild conditions has been developed. Methanol as the solvent proved to be critical for the base-free conditions and high reactivity. A series of linear alkylboronates were synthesized in moderate to excellent yields with high regioselectivity.

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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