Properties and Exciting Facts About 1,1′-Dibenzoylferrocene

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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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Coordination chemistry of perhalogenated cyclopentadienes and alkynes. XXVIII [1] new high-yield synthesis of monobromoferrocene and simplified procedure for the synthesis of pentabromoferrocene. Molecular structures of1,2,3-tribromoferrocene and 1,2,3,4,5-pentabromoferrocene

Monobromoferrocene (1) was obtained in 95% yield from ferrocene via lithiation with tert-BuLi/KO-tert-Bu and bromination with dibromotetrachloroethane. Starting from 1 mixtures of 1,2-dibromoferrocene (2) and apparently unreacted 1 (ranging from 80:20 to 50:50, depending on the reaction conditions) can be obtained via a lithiation- zincation- bromination sequence. These mixtures can be transferred directly with a tenfold excess of Lithium-tetramethylpiperidinide, followed by bromination with 1,1,2,2-tetrabromoethane to pentabromoferrocene (3), in an overall yield of 36% starting from ferrocene. The molecular structures of 3 and of 1,2,3-tribromoferrocene (4) have been determined by X-Ray diffraction.

Coordination chemistry of perhalogenated cyclopentadienes and alkynes. XXVIII [1] new high-yield synthesis of monobromoferrocene and simplified procedure for the synthesis of pentabromoferrocene. Molecular structures of1,2,3-tribromoferrocene and 1,2,3,4,5-pentabromoferrocene

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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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Comparing the reactivity of isomeric phosphinoferrocene nitrile and isocyanide in Pd(ii) complexes: synthesis of simple coordination compounds vs. preparation of P-chelated insertion products and Fischer-type carbenes

Isomeric phosphinoferrocene ligands, viz. 1?-(diphenylphosphino)-1-cyanoferrocene (1) and 1?-(diphenylphosphino)-1-isocyanoferrocene (2), show markedly different coordination behaviours. For instance, the reactions of 1 with [PdCl2(MeCN)2] and [(LNC)Pd(mu-Cl)]2 (LNC = [2-(dimethylamino-kappaN)methyl]phenyl-kappaC1) produced the ?phosphine? complexes [PdCl2(1-kappaP)2] (7) and [(LNC)PdCl(1-kappaP)] (8), and the latter was converted into the coordination polymer [(LNC)Pd(mu(P,N)-1)][SbF6] (9). Conversely, the reaction of 2 with [(LNC)Pd(mu-Cl)]2 involved coordination of the phosphine moiety and simultaneous insertion of the isocyanide group into the Pd-C bond, giving rise to the P,eta1-imidoyl complex [PdCl(Ph2PfcN?CC6H4CH2NMe2-kappa3C,N,P)] (10; fc = ferrocene-1,1?-diyl). Compound 10 was further transformed into the Fischer carbene [PdCl(Ph2PfcN(Me)CC6H4CH2NMe2-kappa3P,C,N)][BF4] (11) by methylation with [Me3O][BF4]. The reactions of 2 with Pd-Me and Pd(eta3-allyl) precursors also led to imidoyl complexes [Pd(mu-Cl)(Ph2PfcN?CR-kappa2C,P)]2 (R = Me: 12, R = allyl: 15), which were cleaved with PPh3 into the corresponding monopalladium complexes [PdCl(PPh3)(Ph2PfcN?CR-kappa2C,P)] (R = Me: 13, R = allyl: 16). The treatment of 12 and 15 with thallium(i) acetylacetonate (acac) produced [Pd(acac-O,O?)(Ph2PfcN?CR-kappa2C,P)] (R = Me: 17, R = allyl: 18). Through proton transfer, these complexes reacted with Ph2PCH2CO2H, ultimately producing bis-chelate complexes [Pd(Ph2PCH2CO2-kappa2O,P)(Ph2PfcN?CR)] (R = Me: 19, R = prop-1-enyl (sic!): 20). In addition, compound 13 was converted into the P-chelated carbene [PdCl(PPh3)(Ph2PfcN(Me)CMe-kappa2C,P)][BF4] (14). Compounds 10, 11, 13 and 14 were studied by cyclic voltammetry and by DFT computations.

Comparing the reactivity of isomeric phosphinoferrocene nitrile and isocyanide in Pd(ii) complexes: synthesis of simple coordination compounds vs. preparation of P-chelated insertion products and Fischer-type carbenes

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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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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: 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 | 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, 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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Reference£º
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 | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion