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A novel ferrocene-containing dianion, Fe(C5H4- CH(CH3)NHCOCH2SO3-)2 (1), has been prepared. The oxidation potential of the PPh4 salt is + 0.35 V (vs. SCE in PhCN), indicating that it is a stronger donor than TTF (tetrathiafulvalene) by + 0.03 V. The dianion provided a TTF salt, the structure and physical properties of which are reported.

A new ferrocene-containing charge-transfer salt, (TTF) 2[Fe(C5H4-CH(CH3)NHCOCH 2SO3)2]

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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 structures adopted by a range of hydrotris(3,5-dimethylpyrazolyl) methane complexes [ML2{HC(pz?)3}]+ (M = Rh, Ir; L2 = diene) have been investigated. There is low steric hindrance between ligands in [Rh(eta-nbd){HC(pz?)3}] + (nbd = norbornadiene) and [Rh(eta-dmbd){HC(pz?) 3}]+ (dmbd = 2,3-dimethylbuta-1,3-diene) resulting in kappa3 co-ordination of the pyrazolylmethane. The complexes [M(eta-cod){HC(pz?)3}]+ (cod = cycloocta-1,5-diene) (M = Rh, Ir) are kappa2 co-ordinated with the free pyrazolyl ring positioned above and approximately parallel to the square plane about rhodium or iridium. The HC(pz?)3 complexes undergo fast exchange of the co-ordinated and unco-ordinated pyrazolyl rings on the NMR spectroscopic timescale. However, for [Rh(eta-dmbd){HC(pz?) 3}]+, the fluxional process is slowed at low temperatures, so that inequivalent pyrazolyl rings may be observed. A mechanism for the fluxional process is proposed involving dynamic interconversion between isomeric forms in solution. The bonding mode of the HC(pz?)3 ligand can be determined by 13C NMR spectroscopy. The 13C chemical shifts (for the sp3 hybridised carbon of the ligand) show the general pattern, kappa3 < 71.5 ppm < kappa2. The electrochemical behaviour of the pyrazolylmethane complexes is related to the degree of structural change, which occurs on electron transfer and is compared with that of the pyrazolylborate analogues. Bonding modes, structures and fluxionality in rhodium and iridium tris(3,5-dimethylpyrazolyl)methane diene complexes The prevalence of solvent effects in heterogeneous catalysis in condensed media has motivated developing theoretical assessments of solvent structures and their interactions with reaction intermediates and transition states. Formula: C14H6FeO2, you can also check out more blogs about1273-94-5

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 compounds with standard potentials ranging from +0.22 to +1.44 V vs SCE were used for inverse photoemission spectroscopy (IPS) studies at the Pt/MeCN interface.Only those couples with standard potentials more positive than +1.0 (+/-0.1) V vs SCE produced inverse photoemission.For species generating emission, the more positive the standard potential, the greater the blue shift in the emission spectra.The wavelength and intensity of the emission spectra also depended on the cathodic limit of the potential pulse.As compared to a Pt electrode, a Rh electrode showed different IPS threshold potentials and weaker IPS emission with electron injection from benzophenone radical anion.

Inverse Photoemission Spectroscopy at Metal/Acetonitrile Interface by Hole Injection through Solution Species

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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 result showed that such a combination of chemo- and biocatalysis improved the catalytic yield more than two times compared with that of sole metal catalysis. We will look forword to the important role of 1273-94-5, and how the biochemistry of the body works.Recommanded Product: 1,1′-Diacetylferrocene

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A unique double ligand-transfer reaction is described for the preparation of substituted cyclopentadienyltricarbonylrhenium complexes. In the reaction, potassium perrhenate(VII) is reduced and carbonylated by treatment with chromium trichloride and chromium hexacarbonyl to provide a proposed alkoxy carbonyl rhenium(I) intermediate. It is believed that this intermediate then undergoes a Cp ligand-transfer reaction with an acyl-substituted ferrocene to provide the corresponding (acyl-cyclopentadienyl)tricarbonylrhenium complex. A strongly coordinating solvent such as methanol is necessary to promote the reduction of perrhenate, and a carbonyl substituent conjugated to the Cp ring is necessary to activate it for transfer from iron to rhenium. This method has potential value for the synthesis of rhenium and technetium organometallic radiopharmaceuticals.

Preparation of cyclopentadienyltricarbonylrhenium complexes using a double ligand-transfer reaction

The result showed that such a combination of chemo- and biocatalysis improved the catalytic yield more than two times compared with that of sole metal catalysis. We will look forword to the important role of 1273-94-5, and how the biochemistry of the body works.Recommanded Product: 1,1′-Diacetylferrocene

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 chromotropic ferrocenyl chalcone with two pyrenyl groups (Fc-dPyr) is prepared and spectroscopically characterized. The X-ray structure analysis shows that the two pyrenyl groups are almost parallel to each other with a torsion angle of 5.57 and adopt a dimeric mode with a distance of 3.776 A? between them, ready to form an excimer. The solvatochromic fluorescence spectra indicate that the emission maxima observed in hydrogen-bonding donor (HBD) solvents (CHCl3, EtOH and MeOH) exhibit a strictly linear relationship with the normalized ETN value, while those in a non-HBD solvent (CH3CN) do not. The molecular chemosensor activity of Fc-dPyr is highly selective toward Fe(III) ions over Fe(II) ions. The fluorescence emission intensity of Fc-dPyr steeply decreases in the presence of Fe(III) ions as an oxidant, but not in the presence of Fe(II) ions.

Chromotropic ferrocenyl chalcone with two pyrenyl groups: Solvatochromism and molecular chemosensor for Fe(III)/Fe(II) ions

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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 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.

Metal-metal charge transfer and solvatochromism in cyanomanganese carbonyl complexes of ruthenium and osmium

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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 first unequivocal examples of intermolecular Friedel-Crafts reactions of ferrocene derivatives proceeding via exo attack of the electrophile are reported. Treatment of 1,1?-bis(trimethylsilyl)-(5a) or 1,1?-bis(tributylstannyl)ferrocene (5b) with acetyl chloride in the presence of AlCl3 affords a mixture of three isomeric acetylferrocenes, 1?-acetyl- (6), 2-acetyl-(7), and 3-acetyl-1-(trialkylsilyl and -stannyl)ferrocene (8). Acetylation of 3,3?-dideutero-1,1?-bis(trimethylsilyl)ferrocene (5aD2) under identical conditions generates the corresponding dideuterated products 6aD2-8aD2. Both 6aD2 and 7aD2 contam 1.0 deuterium atom in each cyclopentadienyl ring whereas 8aD2 contains 05 deutenum atom in the substituted ring and 1.5 deuterium atoms in the “unsubstituted” ring. This demonstrates that the products are formed via exo attack of the electrophile followed by an intramolecular, interannular proton transfer. The lack of scrambling of the deuterium label also suggests that protonation of ferrocenes could also occur through the exo attack of a proton rather than direct protonation at the metal center.

Friedel-crafts acetylation of bis(trimethylsilyl)- and bis(tributylstannyl)ferrocene: implications on the mechanisms of acylation and proton exchange of ferrocene derivatives

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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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Four kinds of mannitol-based ketal-linked porous organic polymers (MKPOPs) were successfully synthesized through condensation reaction between aromatic acetyl monomers and mannitol, catalyzed by p-toluenesulfonic acid. The structure of resulting polymers was confirmed by Fourier transform infrared and solid-state 13C nuclear magnetic resonance spectrum measurements. The porosities of MKPOPs were investigated by gas adsorption experiments and the results indicate high carbon dioxide uptake (up to 11.5 wt% at 273 K and 1.0 bar) for MKPOPs due to the predominant microporous and hydroxyl-rich structures. Remarkably, MKPOPs exhibit excellent selective adsorption performances for carbon dioxide over methane (9.9-14.2, IAST at 273 K and 1.0 bar). These studies are of significant importance for MKPOPs and their potential application in selective gas adsorption.

Preparation of mannitol-based ketal-linked porous organic polymers and their application for selective capture of carbon dioxide

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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 family of heterometallic compounds 3-6 containing ferrocenyl and platinum(ii) centers has been synthesized by reaction of 1-beta- aminoethylferrocene (1) and 1,1?-bis(beta-aminoethyl)ferrocene (2) with Pt(ii) precursors. Using K2[PtCl4] as the Pt(ii) source, the cis-square-planar neutral compounds [Fe{eta5-C 5H4(CH2)2NH2} 2PtCl2] (3) and [{Fe(eta5-C5H 4(CH2)2NH2)(eta5-C 5H5)}2PtCl2] (5) were obtained. Reaction of cis-[PtCl2(dmso)2] with 1 and 2 resulted in the displacement of dmso and chloride ligands from the platinum coordination sphere, affording the cationic and neutral compounds [Fe{eta5- C5H4(CH2)2NH2} 2Pt(dmso)Cl]Cl (4) and [Fe(eta5-C5H 4(CH2)2NH2)(eta5-C 5H5)Pt(dmso)Cl2] (6). Compounds 3-6 were thoroughly characterized using multinuclear (1H, 13C, 195Pt) NMR, IR spectroscopy, ESI mass spectrometry and elemental analysis. Single-crystal X-ray analysis of heterometallic 6 confirmed the cis geometry of the molecule and revealed that the platinum atom is held in a perfect square-planar geometry. The electrochemical behaviour of the heterometallic compounds 3-6, which has been examined by cyclic (CV) and square wave (SWV) voltammetries in dichloromethane and dmso solution, is characterized by the reversible one-electron oxidation of the ferrocene moieties. The results of the biological activity studies revealed that the organometallic complex 5 is active against all cell lines with GI50 values in the range 1.7-2.3 muM. When compared to the standard anticancer drug cisplatin, heterotrimetallic 5, possessing two aminoethylferrocenyl units coordinated to the Pt(ii) center, showed a greater activity profile in the colon cancer cell line. Cell cycle studies revealed that the new mixed compound exhibits a mechanism of action different to cisplatin.

Heterometallic platinum(ii) compounds with beta-aminoethylferrocenes: Synthesis, electrochemical behaviour and anticancer activity

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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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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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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