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Effects of environment on intramolecular electron transfer in mixed-valence 1′,1”’-dinaphthylmethyl(biferrocenium) triiodide: Structural and 57Fe Mossbauer characteristics

Extreme sensitivity to changes in the lattice is observed for electron-transfer rates in the Fe(II)/Fe(III) title compound, as shown by Mossbauer spectroscopic investigations of the two crystallographic phases in which the compound can be isolated. The structure of the cation and anion in the monoclinic phase P21/n is shown on the right.

Effects of environment on intramolecular electron transfer in mixed-valence 1′,1”’-dinaphthylmethyl(biferrocenium) triiodide: Structural and 57Fe Mossbauer characteristics

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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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Highly Reactive Manganese(IV)-Oxo Porphyrins Showing Temperature-Dependent Reversed Electronic Effect in C-H Bond Activation Reactions

We report that Mn(IV)-oxo porphyrin complexes, MnIV(O)(TMP) (1) and MnIV(O)(TDCPP) (2), are capable of activating the C-H bonds of hydrocarbons, including unactivated alkanes such as cyclohexane, via an oxygen non-rebound mechanism. Interestingly, 1 with an electron-rich porphyrin is more reactive than 2 with an electron-deficient porphyrin at a high temperature (e.g., 0 C). However, at a low temperature (e.g., -40 C), the reactivity of 1 and 2 is reversed, showing that 2 is more reactive than 1. To the best of our knowledge, the present study reports the first example of highly reactive Mn(IV)-oxo porphyrins and their temperature-dependent reactivity in C-H bond activation reactions.

Highly Reactive Manganese(IV)-Oxo Porphyrins Showing Temperature-Dependent Reversed Electronic Effect in C-H Bond Activation Reactions

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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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Input of P, N-(phosphanyl, amino)-ferrocene hybrid derivatives in late transition metals catalysis

Unequally functionalized ferrocenes give access to valuable hemilabile reactivity in catalytic reaction. We address the synthesis of hybrid (P, N)-ferrocenyl compounds for which recent catalytic breakthrough applications have been reported, transversely in late transition metals chemistry. Palladium, nickel, rhodium, iridium, and emerging iron and gold catalysis are illustrated from selected examples, which include C?C bond formation from cross-coupling and polymerization, allylic substitution, cyanation, hydroformylation, C?H arylation and silylation and hydrogenation reactions.

Input of P, N-(phosphanyl, amino)-ferrocene hybrid derivatives in late transition metals catalysis

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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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Syntheses and anion binding capabilities of bis(diarylboryl) ferrocenes and related systems

Isomeric diborylated ferrocenes featuring 1,1?-, 1,2-, and 1,3-substitution patterns have been targeted via a combination of electrophilic aromatic substitution and directed ortho-lithiation protocols. While none of these systems are competent for the Lewis acid chelation of fluoride, related systems featuring a mixed B/Si acceptor set capture 1 equiv of fluoride via a Si-F-B bridging motif.

Syntheses and anion binding capabilities of bis(diarylboryl) ferrocenes and related systems

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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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Pronounced effects of crystal structures on intramolecular electron transfer in mixed-valence biferrocenium cations: Structural, EPR, and 57Fe Moessbauer characteristics

Crystallographic properties play an important role in controlling the rate of electron transfer in mixed-valence 1?,1?-disubstituted-biferrocenium triiodide salts. The X-ray structure of neutral 1?,1?-dinaphthylmethylbiferrocene has been determined at 298 K. The corresponding mixed-valence 1?,1?-dinaphthylmethylbiferrocenium triiodide exhibits two crystalline morphologies at 298 K. Dark crystals, formed when a CH2Cl2 solution of triiodide salt was allowed to evaporate slowly, crystallize in space group P1. Dark crystals, obtained when a layer of hexane was allowed to slowly diffuse into a CH2Cl2 solution of triiodide salt, crystallize in monoclinic space group P21/n. The observations of the structural characteristics of 1?,1?-dinaphthylmethylbiferrocenium triiodide are also consistent with our Moessbauer studies. The cation with space group P1 shows two doublets in the variable-temperature Moessbauer spectra at temperatures below 100 K. An increase of temperature causes the two doublets to move together, resulting in an average-valence doublet at 130 K. At 300 K, the spectrum of this sample shows a single doublet which is characteristic of a valence-detrapped cation in which the electron-transfer rate exceeds ?108 s-1. On the other hand, the cation with P21n phase exhibits a Moessbauer spectrum characteric of a valence-trapped cation at 300 K. Obviously, the intramolecular electron-transfer rate is quite sensitive to environment perturbations caused by different crystal packing arrangements. At 77 K, the EPR spectrum of cation with P1 phase is clearly a typical axial-type spectrum with g? = 3.16 and g? = 1.91. Surprisingly, the EPR spectrum of the cation with P21/n phase consists of two g? signals (3.67 and 2.85) and two g? signals (2.01 and 1.79). We suggest that the origin arises from the interaction of spin-spin exchange resulting from a dipole-dipole interaction that develops between cations. The syntheses, characterizations, and physical properties of mixed-valence 1?,1?-di(4-biphenylmethyl)biferrocenium and 1?,1?-di(9-anthracenylmethyl)biferrocenium triiodide salts are also described.

Pronounced effects of crystal structures on intramolecular electron transfer in mixed-valence biferrocenium cations: Structural, EPR, and 57Fe Moessbauer characteristics

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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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I hope this article can help some friends in scientific research. I am very proud of our efforts over the past few months and hope to 1293-65-8, help many people in the next few years.Computed Properties of C10Br2Fe

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Synthesis, crystal structures, electrochemical properties, and complexation of ferrocene-based compounds: 1,2-bis(dimethyldithiocarbamate)ferrocene and 1,2-bis(benzothiazol-2-ylthio)ferrocene

Ferrocene-based metalloligands have various applications in material sciences due to their stability in air and redox active properties. Two ferrocene-based compounds, 1,2-bis(dimethyldithiocarbamate)ferrocene (1) and 1,2-bis(benzothiazol-2-ylthio)ferrocene (2), were synthesized from 1,1?-dibromoferrocene and the corresponding disulfides via two steps. The reaction of 1 with PdCl2(PhCN)2 formed a 1:1 metal:ligand complex, [PdCl2(1)]. Compounds 1, 2, and [PdCl2(1)] were structurally characterized by single-crystal X-ray diffraction, and their redox potentials were measured by cyclic voltammetry. Two pseudopolymorphs, ethanol-solvated 1(C2H5OH)0.33 and non-solvated 1, were obtained by recrystallization from ethanol. The Xray structure of [PdCl2(1)] showed that the Pd(II) center was chelated by 1 with two thioketone sulfur atoms; 1 showed two irreversible oxidationpeaks at 0.17 and 0.41 V (vs. Fe(Cp)2/Fe(Cp)2+), corresponding to oxidation of the two substituents and ferrocene, respectively. Conversely, 2 showed a quasi-reversible redox potential at E1/2 = 0.40 V, attributable to the ferrocene moiety. [PdCl2(1)] showed two irreversible oxidation peaks at 0.48 and 0.64 V and a reduction peak at 0.52 V (vs. Fe(Cp)2/Fe(Cp)2+).

Synthesis, crystal structures, electrochemical properties, and complexation of ferrocene-based compounds: 1,2-bis(dimethyldithiocarbamate)ferrocene and 1,2-bis(benzothiazol-2-ylthio)ferrocene

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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 new facile two-step synthetic procedure of 1,1′-diaminoferrocene

1,1′-Diaminoferrocene (3) was conveniently synthesized by employing a Gabriel synthesis in two steps starting from 1,1′-dibromoferrocene (1). Compound 1 was reacted with 2.5 equivalents of phthalimide in the presence of Cu 2O using 4-picoline as a solvent to give 1,1′-diphthalimidoferrocene (2) in a moderate yield. Hydrazinolysis of 2 in EtOH afforded 3 in good yields of ca. 70%. The subsequent reaction of 3 with two equivalents of ethyloxalyl chloride in THF gave the diethyl ester of N,N’-ferrocenylene bis(oxamic acid) (1,1′-fcbaH2Et2, 4). The solution obtained by treating 4 with two equivalents of n-Bu4NOH in H2O was added to a solution of Pd(AcO)2 in THF to give the palladium complex [n-Bu 4N]2[Pd(1,1′-fcba)] (5) in ca. 80% yield. The compounds 24 were characterized by 1H, 13CNMR and IR spectroscopy as well as elemental analysis and the heterobinuclear complex 5 by 1H NMR and IR spectroscopy, elemental analysis and by a single-crystal X-ray diffraction study.

A new facile two-step synthetic procedure of 1,1′-diaminoferrocene

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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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The synthesis and characterisation of heterosubstituted aminoferrocenes

The synthesis of 1-bromo-1?-aminoferrocene is reported using a simple synthetic methodology. This compound serves as a useful precursor to other heterosubstituted aminoferrocenes. For example, (1?-amino)ferrocenecarboxylic acid has been obtained and is conveniently isolated in its C-protected form by lithiation of 1-bromo-1?-aminoferrocene, quenching with solid carbon dioxide and esterification of the resulting carboxylate with methanolic HCl. The new ligand 1-diphenylphosphino-1?-aminoferrocene has also been obtained using a similar methodology.

The synthesis and characterisation of heterosubstituted aminoferrocenes

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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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Substituent effects in the iron 2p and carbon 1s edge Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy of ferrocene compounds

The iron 2p and carbon 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of substituted ferrocene compounds (Fe(Cp-(CH3) 5)2, Fe(Cp)(Cp-COOH), Fe(Cp-COOH)2, and Fe(Cp-COCH3)2) are reported and are interpreted with the aid of extended Hiickel molecular orbital (EHMO) theory and density functional theory (DFT). Significant substituent effects are observed in both the Fe 2p and C 1s NEXAFS spectra. These effects can be related to the electron donating/withdrawing properties of the cyclopentadienyl ligands and their substituents as well as the presence of pi* conjugation between the cyclopentadienyl ligand and unsaturated substituents.

Substituent effects in the iron 2p and carbon 1s edge Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy of ferrocene compounds

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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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Evaluation of electronics, electrostatics and hydrogen bond cooperative in the binding of cyanide and fluoride by lewis acidic ferrocenylboranes

Synthetic approaches based on the direct borylation of ferrocene by BBr3, followed by boryl substituent modification, or on the lithiation of ferrocene derivatives and subsequent quenching with the electrophile FBMeS2, have given access to a range of ferrocene derivatized Lewis acids with which to conduct a systematic study of fluoride and cyanide binding. In particular, the effects of borane electrophilicity, net charge, and ancillary ligand electronics/cooperativity on the binding affinities for these anions have been probed by a combination of NMR, IR, mass spectrometric, electrochemical, crystallographic, and UV-vis titration measurements. In this respect, modifications made at the para position of the boron-bound aromatic substituents exert a relatively minor influence on the binding constants for both fluoride and cyanide, as do the electronic properties of peripheral substituents at the 1 ?- position (even for cationic groups). By contrast, the influence of a CH2NMe3 + substituent in the 2- position is found to be much more pronounced (by >3 orders of magnitude), reflecting, at least in part, the possibility in solution for an additional binding component utilizing the hydrogen bond donor capabilities of the methylene CH2 group. While none of the systems examined in the current study display any great differentiation between the binding of F- and CN- (and indeed some, such as FcBMeS2, bind both anions with equal affinity within experimental error), much weaker boronic ester Lewis acids will bind fluoride (but give a negative response for cyanide). Thus, by the incorporation of an irreversible redox-matched organic dye, a two-component [BMes2/B(OR)2] dosimeter system can be developed capable of colorimetrically signaling the presence of fluoride and cyanide in organic solution by Boolean AND/NOT logic.

Evaluation of electronics, electrostatics and hydrogen bond cooperative in the binding of cyanide and fluoride by lewis acidic ferrocenylboranes

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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