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The complexes [(H3N)5RuII(-NC)Mn ILx]2+, prepared from [Ru(OH 2)(NH3)5]2+ and [Mn(CN)L x] {Lx = trans-(CO)2{P(OPh)3}(dppm); cis-(CO)2(PR3)(dppm), R = OEt or OPh; (PR 3)(NO)(eta-C5H4Me), R = Ph or OPh}, undergo two sequential one-electron oxidations, the first at the ruthenium centre to give [(H3N)5RuIII(-NC)MnIL x]3+; the osmium(iii) analogues [(H3N) 5OsIII(-NC)MnILx]3+ were prepared directly from [Os(NH3)5(O3SCF 3)]2+ and [Mn(CN)Lx]. Cyclic voltammetry and electronic spectroscopy show that the strong solvatochromism of the trications depends on the hydrogen-bond accepting properties of the solvent. Extensive hydrogen bonding is also observed in the crystal structures of [(H 3N)5RuIII(-NC)MnI(PPh 3)(NO)(eta-C5H4Me)][PF6] 3·2Me2CO·1.5Et2O, [(H 3N)5RuIII(-NC)MnI(CO)(dppm) 2-trans][PF6]3·5Me2CO and [(H3N)5RuIII(-NC)MnI(CO) 2{P(OEt)3}(dppm)-trans][PF6] 3·4Me2CO, between the ammine groups (the H-bond donors) at the Ru(iii) site and the oxygen atoms of solvent molecules or the fluorine atoms of the [PF6]- counterions (the H-bond acceptors). The Royal Society of Chemistry 2006.

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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 cesium fluoride-promoted reductive coupling reaction of acylferrocene tosylhydrazones with arylboronic acids has been developed, producing highly substituted alpha-arylalkylferrocenes in moderate to excellent yields. The reaction employs anionic fluorine to facilitate the cleavage of C?B bond. The developed methodology demonstrates a wide substrate scope and high functional groups tolerance. Moreover, the alpha-arylalkylferrocenes compounds were also obtained on a multi-gram scale.

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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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Molecular or supramolecular level photoluminescence (PL) modulation combining chemical and photonic input/output signals together in an integrated system can provide potential high-density data memorizing and process functions intended for miniaturized devices and machines. Herein, a PL-responsive supramolecular coordination cage has been demonstrated for complex interactions with redox-active guests. PL signals of the cage can be switched and modulated by adding or retracting Fc derivatives or converting TTF into different oxidation states through chemical or photochemical pathways. As a result, reversible or stepwise PL responses are displayed by these host?guest systems because of the occurrence of photoinduced electron-transfer (PET) or fluorescence resonance energy transfer (FREnT) processes, providing unique nanodevice models bearing off/on logic gates or memristor-like sequential memory and Boolean operation functions.

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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 novel solvent free synthetic method has been designed by using rice husk ash (RHA) as solid support for the selective functionalization of ferrocenyl derivatives and described the synthesis of a 1,1?-unsymmetrically bi-functionalized ferrocenyl compounds for their biological evaluation. Single crystal X-ray structural evaluation showed some interesting intra-molecular hydrogen bonding interactions across the chains of the ferrocenyl molecule, while DFT calculation revealed the significance of the orientation between the two cyclopentadienyl rings for the hydrogen bonding interaction. Redox and antibacterial properties have been studied to understand the electronic and biological effect of different hydrazone system and their potential for future application.

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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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Transition-metal complexes of radical ligands can exhibit low-energy electronic transitions in the near-infrared (NIR) spectral region. NIR band energy and intensity sensitively depend on the degree of electronic coupling of the chromophore. Using the example of open-shell complexes derived from platinum and a 1,4-terphenyldithiophenol, we present a novel approach toward spectroscopically distinct NIR dyes for which the degree of electronic coupling correlates with the relative orientation of radical ligand and metal orbitals. Ligand/metal orbital alignment is modulated by auxiliary phosphine donors and selectively results in electron localized Class II-III or delocalized Class III structures that display distinct NIR transitions at 6500 and 4000 cm-1

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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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On treatment with glyoxylic acid and hydrazine hydrate, 1,1?-diacetylferrocene was converted into the separable mixture of 1,1?-bis [pyridazin-3(2H)-one-6-yl]ferrocene and the hydrazone as well as the azine of 1-acetyl-1?-[pyridazin-3(2H)-one-6-yl]ferrocene. Successful cyclizations of 1,1?-bis[pyridazin-3(2H)-one-6-yl]ferrocene resulting in a series of novel ferrocenophanes containing heterocyclic units were performed under phase transfer- and homogeneous catalytic (RCM) conditions by the application of versatile dialkylating agents and second generation Grubbs’ catalyst, respectively. The structures were determined by mass spectrometry, IR, 1H and 13C NMR spectroscopy including 2D-COSY, HMQC and HMBC measurements. The solid phase structure of a dimer product with pi-stacking interaction was revealed by X-ray analysis.

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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 complex [Rh(CO)2{HC(pz?)3}][PF6], 1 +[PF6]- {HC(pz?)3 = tris(3,5-dimethylpyrazolyl)methane}, prepared by reacting [{Rh(CO)2(mu-Cl)}2] with HC(pz?)3 in the presence of Tl[PF6], has a distorted square pyramidal structure with a kappa3-HC(pz?)3 ligand. Carbonyl substitution with Lewis bases gives [Rh(CO)L{HC(pz?)3}] [PF6] {L = PPh3, 2+[PF6]-; L = AsPh3, 3+[PF6]-; L = P(o-tolyl)3, 4+[PF6]-}, which have square planar kappa2 structures, confirmed by X-ray crystallography for 2+[PF6]-. The cations 2+ and 3+ have the third pyrazolyl ring orientated pseudo-parallel to the square planar metal whereas 4+ more likely has the third ring orientated exo to that plane. One-electron oxidation of 2+ and 3+ gives the Rh(II) dications [Rh(CO)(PPh3){HC(pz?)3}]2+, 22+, and [Rh(CO)(AsPh3){HC(pz?)3}]2+, 32+, characterised by ESR spectroscopy. Complex 1+[PF6]- reacts with PhC?CPh to give [Rh(CO)(eta2-PhC?CPh)-{HC(pz?)3}] [PF6], 5+[PF6]-, in which the two-electron donor alkyne occupies an equatorial position in a trigonal bipyramidal kappa3 structure. With MeC?CR (R = Me or Et), 1+[PF6]- gives the kappa2 square planar complexes [Rh{eta4-C4Me2R2C(O)}{HC(pz? )3}][PF6] (R = Me, 6+[PF6]-; R = Et, 7+[PF6]-) in which the cyclopentadienone ligands are coordinated via two Rh-monoalkene bonds; the structurally characterised form of 7+ has the two alkyne units linked head-to-head with the CEt termini bound to the ketonic CO group. With HC?CPh or HC?CH, 1+ gives the octahedral, kappa3 rhodium(III) metallacyclopentadienes [Rh(CO)(eta1:eta1?-CHCRCHCR) {HC(pz?)3}][PF6] (R = Ph, 8+[PF6]-; R = H, 9+[PF6]-) with the two alkynes linked head-to-tail in 8+. The reaction of 1+ with HC?CH also gives the cycloheptatrienone (tropone) derivative [Rh{eta4-C6H6C(O)}{HC(pz?)3} ][PF6], 10+[PF6]-, with a kappa3 ligand and the cycloheptatrienone ligand bound to the metal via two Rh-C sigma-bonds and one Rh-monoalkene interaction.

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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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Ferrocenes bearing acyl substituents in the cyclopentadienyl rings [Fe(eta5-C5H4COR)(eta5-C 5H5)] and [Fe(eta5-C5H 4COR)2] (R = CH3, CF3 and Ph) were examined as new driers for solvent-borne alkyd binder. All studied ferrocenes were found to be active catalysts for cross-linking reaction of the alkyd. These iron(II) compounds give solid polymeric films with hardness and drying time comparable to the commercial cobalt(II) drier. Acetyl- and benzoyl-substituted ferrocenes show an excellent synergic effect with the cobalt drier giving hard polymeric films within short drying time. The kinetics of the alkyd autoxidation was followed by FTIR spectroscopy. Spin-trapping ESR technique has proven the important role of the ferrocenium cation upon decomposition of hydroperoxides by ferrocene-based driers. The peroxy and alkoxy radicals, appearing in drying process, were resolved by the new spin trap methyl-N-mesityl nitrone.

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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 t-butyl and bis(t-butyl) derivatives of hexathia[3.3]ferrocenophane were prepared from the corresponding trithia[3]ferrocenophanes. The former was a mixture of chair-chair and chair-boat isomers, and the latter existed only chair-boat isomer. The hexathia[3.3]ferrocenophanes were led to the tetrathiols with LiAlH4, which allowed to react with 1,1?-thiocarbonyldiimidazol to give the corresponding ferroceno[1?,2?;1?,2?]bis(1,3-dithiol-2-thione) derivatives. Mono t-butyl and unsubstituted analogs were prepared in a similar manner. The X-ray structural determination showed that these derivatives adopted the conformation in which the 1,3-dithiol-2-thione rings were heaped on top of each other. In the crystal of ferroceno[1?,2?;1?,2?]bis(1,3-dithiol-2-thione), the molecules packed so as to put the axis of molecule in order and to overlap one another above and below. The desulfurizative coupling of the ferroceno[1?,2?;1?,2?]bis(1,3-dithiol-2-thione) derivatives was unsuccessful.

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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 ruthenium(II) ferrocenyl heterocyclic thiosemicarbazone complexes of the type [RuCl(CO)(EPh3)]2L (where E = P/As; L = binucleating monobasic tridendate thiosemicarbazone ligand) have been investigated. Strutural features were determined by analytical and spectral techniques. Binding of these complexes with CTDNA by absorption spectral study indicates that the ruthenium(II) complexes form adducts with DNA and has intrinsic binding constant in the range of 3.3 × 104 – 1.2 × 105 M?1. The complexes exhibit a remarkable DNA cleavage activity with CT-DNA in the presence of hydrogen oxide and the cleavage activity depends on dosage.

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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