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Redox control of a dendritic ferrocenyl-based homogeneous catalyst

The application of a dendrimer in a redox-switchable catalytic process is reported. A monomeric and the corresponding dendritic ferrocenylphosphane ligand were used to develop well-defined controllable catalysts with distinct redox states. The corresponding ruthenium(II) complexes catalyze the isomerization of the allylic alcohol 1-octen-3-ol. By adding a chemical oxidant or reductant, it was possible to reversibly switch the catalytic activity of the complexes. On oxidation, the ferrocenium moiety withdraws electron density from the phosphane, thereby lowering its basicity. The resulting electron-poor ruthenium center shows much lower activity for the redox isomerization and the reaction rate is markedly reduced.

Redox control of a dendritic ferrocenyl-based homogeneous catalyst

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Platinum complexes of a borane-Appended Analogue of 1,1′-Bis(diphenylphosphino)ferrocene: Flexible borane coordination modes and in situ vinylborane formation

A bis(phosphine)borane ambiphilic ligand, [Fe(h5-C5H4PPh2)(h5-C5H4PtBu{C6H4 (BPh2)-ortho})] (FcPPB), in which the borane occupies a terminal position, was prepared. Reaction of FcPPB with tris(norbornene)platinum(0) provided [Pt(FcPPB)] (1) in which the arylborane is h3BCC-coordinated. Subsequent reaction with CO and CNXyl (Xyl=2,6-dimethylphenyl) afforded [PtL(FcPPB)] {L=CO (2) and CNXyl (3)} featuring h2BC-And h1B-Arylborane coordination modes, respectively. Reaction of 1 or 2 with H2 yielded [PtH(m-H)(FcPPB)] in which the borane is bound to a hydride ligand on platinum. Addition of PhC2H to [Pt(FcPPB)] afforded [Pt(C2Ph)(m-H)(FcPPB)] (5), which rapidly converted to [Pt(FcPPB’)] (6; FcPPB’=[Fe(h5-C5H4PPh2)(h5- C5H4PtBu{C6H4 (BPh-CPh=CHPh-Z)-ortho}]) in which the newly formed vinylborane is h3BCC-coordinated. Unlike arylborane complex 1, vinylborane complex 6 does not react with CO, CNXyl, H2 or HC2Ph at room temperature.

Platinum complexes of a borane-Appended Analogue of 1,1′-Bis(diphenylphosphino)ferrocene: Flexible borane coordination modes and in situ vinylborane formation

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Studies on the cyclomercuration of 1,1?-bis[(arylimino)phenylmethyl]ferrocenes

The reaction of bisferrocenylimines with mercuric acetate and subsequent treatment with LiCl lead to formation of mono (9) and double (10) cyclomercurated derivatives. The 1H NMR and 199Hg NMR spectra of the double cyclomercurated bisferrocenylimines show that compounds 10 exist as two isomers (meso and dl). The individual stereoisomers were isolated successfully by crystal picking. The structures of these new compounds have been confirmed by elemental analysis, IR and 1H NMR spectroscopies, and further by X-ray crystal structure determination of meso [{HgCl(eta5-C5H3CPh=NAr)}2Fe] (Ar=m-CH3C6H4).

Studies on the cyclomercuration of 1,1?-bis[(arylimino)phenylmethyl]ferrocenes

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Facile syntheses of dissymmetric ferrocene-functionalized Lewis acids and acid-base pairs

A facile synthetic approach is reported for the synthesis of dissymmetric 1,2-ferrocenediyl Lewis acids and mixed acid-base pairs including the first example of a 1-phosphino-2-borylferrocene; the use of non-racemic electrophiles allows for the isolation of single diastereomer products.

Facile syntheses of dissymmetric ferrocene-functionalized Lewis acids and acid-base pairs

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Stereospecific synthesis, structural characterisation and resolution of 2-phospha[3]ferrocenophane derivatives – A new chiral scaffold

The first 2-phospha[3]ferrocenophanes containing stereogenic carbon atoms in the three-atom bridge have been synthesised from phenylphosphane by stereospecific ring-closing phosphanation reactions. Either alpha-substituted 1,1?-bis-(hydroxymethyl)ferrocenes or the corresponding 2-oxa-[3]ferrocenophanes have been used as diastereomerically pure starting materials. The resolution of 1,2,3-triphenyl-[2]phosphaferrocenophane has been achieved by chromatographic separation of the diastereomeric adducts of a chiral cyclopalladate complex. The X-ray crystal structures of two 2-phospha[3]ferrocenophane-borane complexes are also reported. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Stereospecific synthesis, structural characterisation and resolution of 2-phospha[3]ferrocenophane derivatives – A new chiral scaffold

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Synthesis of Two Isomeric Ferrocene Phosphanylcarboxylic Acids and their PdII Complexes with and without Auxiliary ortho-Metalated C,E-Ligands (E = N and S)

Two homologous ferrocene phosphanylcarboxylic acids, viz., 1?-[(diphenylphosphanyl)methyl]ferrocene-1-carboxylic acid (HL1) and [1?-(diphenylphosphanyl)ferrocenyl]acetic acid (HL2), were synthesized and studied as ligands in PdII complexes. The addition of these hybrid donors to [PdCl2(MeCN)2] led to the bis-phosphane complexes trans-[PdCl2(HL1-kappaP)2] and trans-[PdCl2(HL2-kappaP)2]. In contrast, the reactions of HL1 and HL2 with the PdII acetylacetonate (acac) complexes [(LYC)Pd(acac)], where LYC = 2-[(dimethylamino-kappaN)methyl]phenyl-kappaC1 (LNC) and 2-[(methylthio-kappaS)methyl]phenyl-kappaC1 (LSC), proceeded under proton transfer and replacement of the acac ligand, giving rise to O,P-bridged phosphanylcarboxylate dimers [LYCPd(mu(P,O)-L1)]2 and molecular chelates [LYCPd(L2-kappa2O,P)]2, respectively. The analogous reactions involving 1?-(diphenylphosphanyl)-1-ferrocenecarboxylic acid (Hdpf) provided the macrocyclic tetramer [LNCPd(mu(P,O)-dpf)]4 and the dimer [LSCPd(mu(P,O)-dpf)]2. The reactions of HL1 with [Pd(acac)2] only led to an ill-defined, insoluble material, whereas those with HL2 produced a separable mixture of the bis-chelate complexes trans-[Pd(L2-kappa2O,P)2], cis-[Pd(L2-kappa2O,P)2], and [Pd(acac)(L2-kappa2O,P)].

Synthesis of Two Isomeric Ferrocene Phosphanylcarboxylic Acids and their PdII Complexes with and without Auxiliary ortho-Metalated C,E-Ligands (E = N and S)

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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ELECTRONIC STRUCTURE OF HALOGENOFERROCENES STUDIED BY He(I) PHOTOELECTRON SPECTROSCOPY

He(I) photoelectron (PE) spectra are reported for chloroferrocene Fe(eta-C5H4Cl)(eta-C5H5) and 1,1′-dihalogenoferrocenes Fe(eta-C5H4X)2 (X=Cl, Br).The difference between the ionization potentials (IP’s) of the e2g(d) and a1g(d) level is not affected by the ring substitution.Only the splitting of the e1u(?) level of the ligand is observed in the spectra.From the magnitudes of the splittings of this level and halogen non-bonding orbitals it is concluded that there is significant mixing of iron p orbitals with the e1u(?) level.The spectrum of Fe(eta-C5H4Cl)2 indicates that there is an interaction between the non-bonding out-of-plane chlorine p orbitals.

ELECTRONIC STRUCTURE OF HALOGENOFERROCENES STUDIED BY He(I) PHOTOELECTRON SPECTROSCOPY

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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 influence on charge transfer interactions in alpha,alpha?-Diferrocenylthiophenes

Within a series of alpha,alpha?-diferrocenylthiophenes, the influence of electron-withdrawing substituents at the ferrocenyl moieties and electron-donating functionalities at the thiophene bridge on the electronic behavior was studied. The synthesis of the appropriate 2,5-fc2-cC4H2S and 2,5-fc2-3,4-(OCH2CH2O)-cC4S compounds (fc = Fe(eta5-C5H4)(eta5-C5H4R); R = H (1, 5), 3,5-(CF3)2-cC6H3 (2, 6), CHO (3, 7), C?N (4, 8)) was carried out using the Negishi C,C cross-coupling protocol to effect the coupling of the thiophene and the ferrocenyl moieties. The corresponding diferrocenylthiophenes were characterized spectroscopically. Within this context, the structural properties of 2-5, [5][B(C6F5)4], 6, and 8 in the solid state were investigated by single-crystal X-ray diffraction studies. Electrochemical investigations of thiophenes 2-8 demonstrated an increasing redox separation and hence thermodynamic stability of the corresponding mixed-valent species in the series 1 < 3 < 5 < 4 ? 2 < 6 < 7 < 8. Moreover, UV/vis/near-IR and infrared spectroelectrochemical studies verify these observations. These studies further reveal a valence trapped situation in corresponding mixed-valent species and allow a class II classification according to Robin and Day. (Figure Presented) Substituent influence on charge transfer interactions in alpha,alpha?-Diferrocenylthiophenes 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 1293-65-8, and how the biochemistry of the body works.Related Products of 1293-65-8

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Acceptor-substituted ferrocenium salts as strong, single-electron oxidants: Synthesis, electrochemistry, theoretical investigations, and initial synthetic application

A series of mono- and 1,1′-diheteroatom-substituted ferrocene derivatives as well as acylated ferrocenes was prepared efficiently by a unified strategy that consists of selective mono- and 1,1′-dilithiation reactions and subsequent coupling with carbon, phosphorus, sulfur and halogen electrophiles. Chemical oxidation of the ferrocene derivatives by benzoquinone, 2,3-dichloro-5,6- dicyanobenzoquinone, AgPF6, or 2,2,6,6-tetramethyl-1-oxopiperidinium hexafluorophosphate provided the corresponding ferrocenium salts. The redox potentials of the synthesized ferrocenes were determined by cyclic voltammetry, and it was observed that all new ferrocenium salts have stronger oxidizing properties than standard ferrocenium hexafluorophosphate. An initial application of selected derivatives in an oxidative bicyclization revealed that they mediate the transformation under considerably milder conditions than ferrocenium hexafluorophosphate. Quantum chemical calculations of the reduction potentials of the substituted ferrocenium ions were carried out by using a standard thermodynamic cycle that involved the gas-phase energetics and solvation energies of the contributing species. A remarkable agreement between theory and experiment was found: the mean average deviation amounted to only 0.030-V and the maximum deviation to 0.1-V. This enabled the analysis of various physical contributions to the computed reduction potentials of these ferrocene derivatives, thereby providing insight into their electronic structure and physicochemical properties. Copyright

Acceptor-substituted ferrocenium salts as strong, single-electron oxidants: Synthesis, electrochemistry, theoretical investigations, and initial synthetic application

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The design and synthesis of a new potentially C3-symmetric ferrocenylphosphine

A new potentially C3-symmetric phosphine ligand ‘manphos’ has been obtained and fully characterized. The ligand which is a tri-ferrocenyl-tetra-phosphine is obtained in a simple and effective two step synthesis starting from 1,1?-dibromoferrocene via the intermediate compound tris-(1?-bromoferrocenyl)phosphine or alternatively via 1′-bromo-1-diphenylphosphinoferrocene. The iso -propylphosphino-analogue of manphos, tris-(1′-diisopropylphosphinoferrocenenyl)phosphine, has also been obtained, in addition to several functionalised derivatives of triferrocenylphosphine where the ferrocene rings have been substituted in the 1?-position.

The design and synthesis of a new potentially C3-symmetric ferrocenylphosphine

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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