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Unique Deuterium Exchange Reaction in Certain Substituted Ferrocenes

Deuterium exchange of certain substituted ferrocenes (under very mild basic conditions) occurs in only the substituted cyclopentadienyl-ring in non-statistical pattern; a ?->? (eta5->eta1) rearrangement mechanism is proposed to account for the novel pattern of exchange.

Unique Deuterium Exchange Reaction in Certain Substituted Ferrocenes

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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 Mononuclear Non-heme Manganese(III)-Aqua Complex as a New Active Oxidant in Hydrogen Atom Transfer Reactions

A mononuclear non-heme Mn(III)-aqua complex, [(dpaq)MnIII(OH2)]2+ (1, dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate), is capable of conducting hydrogen atom transfer (HAT) reactions much more efficiently than the corresponding Mn(III)-hydroxo complex, [(dpaq)MnIII(OH)]+ (2); the high reactivity of 1 results from the positive one-electron reduction potential of 1 (Ered vs SCE = 1.03 V), compared to that of 2 (Ered vs SCE = -0.1 V). The HAT mechanism of 1 varies between electron transfer followed by proton transfer and one-step concerted proton-coupled electron transfer, depending on the one-electron oxidation potentials of substrates. To the best of our knowledge, this is the first example showing that metal(III)-aqua complex can be an effective H-atom abstraction reagent.

A Mononuclear Non-heme Manganese(III)-Aqua Complex as a New Active Oxidant in Hydrogen Atom Transfer Reactions

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

 

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Formation of functionalized [3]ferrocenophane derivatives by an enamine condensation reaction

Treatment of 1,1?-diacetylferrocene (10) with excess piperidine and a stoichiometric amount of TiCl4 in pentane leads to CC-coupling of the two functional groups at the ferrocene framework. This enamine condensation reaction leads to the formation of the 1,3-connected dienamine-bridged [3]ferrocenophane system 13a. Complex 13a was characterised by X-ray crystal structure analysis. The analogous TiCl4-mediated coupling and condensation reactions of 10 with morpholine, pyrrolidine or methyl-isopropylamine yield the corresponding substituted [3]ferrocenophane systems 13b-d.

Formation of functionalized [3]ferrocenophane derivatives by an enamine condensation reaction

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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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1,1?-Bis(pyrazol-3-yl)ferrocene: A Clip Ligand That Forms Supramolecular Aggregates and Prismatic Hexanuclear Coinage Metal Complexes

Two ferrocene derivatives with appended pyrazole substituents, namely, 1,1?-bis(5-methyl-1H-pyrazol-3-yl)ferrocene (H2LH) and 1,1?-bis(5-trifluoromethyl-1H-pyrazol-3-yl)ferrocene (H2LF), were synthesized. In solid state they form distinct H-bonded dimers with orthogonal (H2LH, C2 symmetry) or antiparallel (H2LF, C2h symmetry) arrangement of the two ferrocene/pyrazole hybrid molecules. Supramolecular dimerization was also detected in solution at low temperatures, though diffusion-ordered spectroscopy and variable-temperature NMR spectroscopy revealed several dynamic processes. Redox potentials of the ferrocene derivatives are affected by the nature of the pyrazole substituent (Me, CF3). In their deprotonated form [LR]2-, both ferrocene/pyrazole hybrids serve as ligands and form oligonuclear CuI, AgI, and AuI complexes that were identified by matrix-assisted laser desorption ionization mass spectrometry. X-ray crystallography revealed the structures of Cu6L3H and Ag6L3F, which both contain two parallel and eclipsed [M(mu-pz)]3 metallamacrocycles (M = Cu, Ag) linked by three ferrocene units. MI…MI distances between the two triangular M3N6 decks are shorter in Ag6L3F (3.28-3.30 vs 3.44-3.51 A in the case of Cu6L3H), indicating substantial intramolecular closed-shell Ag(d10)-Ag(d10) interactions. However, Cu6L3H features close intermolecular Cu…Cu contacts as short as 3.37 A. Moessbauer data for both the ligands and complexes were collected, and electrochemical properties were measured; preliminary luminescence data are reported. (Figure Presented).

1,1?-Bis(pyrazol-3-yl)ferrocene: A Clip Ligand That Forms Supramolecular Aggregates and Prismatic Hexanuclear Coinage Metal Complexes

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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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Self-assembly of conducting cocrystals: Via iodine?pi(Cp) interactions

Conducting crystals of alternating ferrocene and diiodoacetylene units assembled into supramolecular 1-D chains via I?pi(Cp) halogen bonds were prepared and structurally characterized. Their structure and conductivity were compared with the ferrocene cocrystals with phenyliodoacetylene (C6H5C2I) and 1,4-di(ethynyliodo)phenylene. Electrical conductivity measurements of the ferrocene-based cocrystals revealed comparatively high electron-hole type conductivity in the ferrocene (FcH)-diiodoacetylene (C2I2) pair, a 3-order decrease in combination with the 1,4-di(ethynyliodo)phenylene linker, and it is virtually extinguished with the monotopic 1,2-phenyliodoacetylene. The increased electric conductivity of compound 1 is rationalized in terms of a weak charge transfer through the I?piCp halogen bonds in the [Cp-Fe-Cp?I-CC-I?]n polymeric chains.

Self-assembly of conducting cocrystals: Via iodine?pi(Cp) interactions

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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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Synthesis and characterization of novel ferrocenyl heterocyclic compounds

An efficient synthetic approach to the synthesis of ferrocenyl heterocyclic derivatives in dilute solutions has been developed. The new compounds were characterised by means of IR, UV, and 1H NMR, spectroscopy and elemental analysis. The structure of complex I was studied by X-ray single-crystal diffraction. The synthesized compounds have a potential of new enzyme models and molecular recognition hosts.

Synthesis and characterization of novel ferrocenyl heterocyclic compounds

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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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Thiomethoxychalcone-functionalized ferrocene ligands as selective chemodosimeters for mercury(II): Single-crystal X-ray structural signature of the [Hg8(mu8-S)(SCH3)12] 2+ cluster

Thiomethoxychalcone-based ligands bis[3,3-bis(methylsulfanyl)]-1,1?- eta5-ferrocenyl-2-propen-1-one (L1), 3,3-bis(methylsulfanyl)-1-eta5-ferrocenyl-2-propen-1-one (L 2), and 3-methylsulfanyl-3-sulfanyl-1-eta5-ferrocenyl-2- propen-1-one (L3) have been synthesized on the ferrocene backbone by varying the number of chalcone arms and thiomethoxy substitutents. The single-crystal X-ray crystallographic analyses of all three ligands are reported in which crystals of L1 were obtained as both syn and anti conformers and showed the conformational freedom of the two cyclopentadienyl (Cp) units. L1-L3 are studied extensively toward their applicability in the colorimetric sensing of metal ions in solution. The solution-state study of mono- and bis(thiomethoxy)ferrocenylchalcone- functionalized ligands L1 and L2 showed selective colorimetric sensing for Hg2+ over Li+, Na+, Ca2+, Mg2+, Cr2+, Mn2+, Fe 2+, Co2+, Ni2+, Cu2+, Zn 2+, Cd2+, and Au3+ in acetonitrile. In both cases, a selective color change from orange to purple was observed with Hg 2+ and the resultant solution showed the appearance of a new peak at 565 nm (epsilon = 3920 M-1 cm-1) for L1 and 600 nm (epsilon = 1140 M-1 cm-1) for L2 in the UV/vis experiments. The UV/vis titration profiles of L1 and L 2 indicate the formation of 2:1 (L1/Hg2+) and 1:1 (L2/Hg2+) initial complexations in solution. On the other hand, L3 with thiomethoxy- and thiol-functionalized ferrocenylchalcone showed no appreciable color change with Hg2+ under the same experimental conditions. Attempts were made to isolate single crystals of the resulting purple solution obtained in the cases of L1 and L2 with Hg2+. In both cases, crystals suitable for a single-crystal X-ray diffraction study were isolated in very low yield by a layer diffusion technique. The single-crystal structural investigations demonstrated the formation of a sulfide-encapsulated mercury thiolate cuboctahedron cluster, [Hg8S(SCH3)12] 2+, upon a selective chemodosimetric desulfurization reaction between Hg2+ and L1 or L2. Cyclic voltammetric studies also support the Hg2+-induced cleavage of thiomethoxy groups.

Thiomethoxychalcone-functionalized ferrocene ligands as selective chemodosimeters for mercury(II): Single-crystal X-ray structural signature of the [Hg8(mu8-S)(SCH3)12] 2+ cluster

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

 

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Synthesis of ferrocene-containing dichalcones

Condensation of 1,11-diacetylferrocene with mono- and disubstituted benzaldehydes in 96% ethanol in the presence of sodium hydroxide has afforded ferrocene-containing dichalcones.

Synthesis of ferrocene-containing dichalcones

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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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Synthesis of <3.3>(1,1′)- and <5.5>(1,1′)Ruthenocenophanes and Their Ferrocenoruthenocenophane Homologs

<3.3>(1,1′)Ruthenocenophane-2,14-diene-1,16-dione, <5.5>(1,1′)ruthenocenophane-2,14,17,29-tetraene-1,16-dione and their ferrocenoruthenocenophane homologs were synthesized by using an intramolecular base-catalyzed condensation.

Synthesis of <3.3>(1,1′)- and <5.5>(1,1′)Ruthenocenophanes and Their Ferrocenoruthenocenophane Homologs

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Structural features of lithio[3]ferrocenophane systems bearing stabilizing dimethylamino substituents

Treatment of the a-dimethylamino[3]ferrocenophane derivative 3 with n-butyllithium results in a directed o-metalation at the adjacent Cp ring of the ferrocene unit to selectively yield the (R*,R*,p-S*) diastereomer 4. Similarly, lithiation of rac-12 gives (R*,p-S*)-13. Both these compounds form mesc-type dimers in the crystal that feature a central C2Li2 four-membered-ring moiety. Compound 13 crystallizes with excess n-butyllithium to form a (13-n-BuLi) dimer that was also characterized by X-ray diffraction. Directed lithiation of the nonbridged ferrocene derivative l-(dimethylaminobenzyl)ferrocene (16) with tertbutyllithium resulted in an opposite stereoselectivity to yield (R*,p-R*)-17, which forms a chiral dimeric structure in the solid state, as was revealed by its X-ray crystal structure analysis.

Structural features of lithio[3]ferrocenophane systems bearing stabilizing dimethylamino substituents

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