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A novel polar dppf derivative possessing only planar chirality, 1?,2-bis(diphenylphosphino)-ferrocene-1-carboxylic acid (Hdpc), has been synthesised in racemic form and resolved into enantiomers via esters with d-glucose diacetonide ((Rp)- and (Sp)-3). (R p)-Hdpc was further converted to a series of N-substituted amides that were studied as ligands for Pd-catalysed enantioselective allylic alkylation of racemic (E)-1,3-diphenylprop-2-en-1-yl acetate or ethyl carbonate with malonate esters, showing high activity and good enantioselectivity (er up to 10: 90). The catalytic results were correlated with the structural data (X-ray diffraction and solution NMR) for (eta3-allyl)palladium(ii) complex (Rp)-[Pd(eta3-1,3-Ph2C 3H3){Fe(eta5-C5H 3-1-(C(O)NHCH2Ph)-2-(PPh2-kappaP)) (eta5-C5H4PPh2-kappaP)}]ClO 4 (16) as a model of the plausible reaction intermediate. A further study into the coordination properties of Hdpc led to isolation of chelate complex [PdCl2(Hdpc-kappa2P,P?)] (12). The crystal structures of rac-Hdpc, methyl ester of (Rp)-Hdpc, glycoside (R p)-3, and 12·Me2CO suggested a close structural relationship between dppf and Hdpc. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2009.

Preparation, coordination and catalytic use of planar-chiral monocarboxylated dppf analogues

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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

 

Archives for Chemistry Experiments of 1,1′-Dibromoferrocene

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Ligands of the formula (I) secondary phosphine-Q-P(=O)HR1 (I) in the form of mixtures of diastereomers or pure diastereomers, in which secondary phosphine is a secondary phosphine group with hydrocarbon radicals or heterohydrocarbon radicals as substituents; Q is a bivalent bisaryl or bisheteroaryl radical with an axial chiral centre to which the two phosphorus atoms are bonded in the ortho positions to the bisaryl or bisheteroaryl bridge bond, or Q is a bivalent ferrocenyl radical with a planar chiral centre or without a planar chiral centre, to which the phosphorus atom of the secondary phosphine is bonded directly or via a C1-C4-carbon chain to a cyclopentadienyl ring, the -P*(=O)HR1 group is bonded either on the same cyclopentadienyl ring in ortho position to the bonded secondary phosphine or on the other cyclopentadienyl ring; P* is a chiral phosphorus atom, and R1 is a hydrocarbon radical, a heterohydrocarbon radical or a ferrocenyl radical, where R1 is a ferrocenyl radical with a planar chiral centre when Q is a ferrocenyl radical without a planar chiral centre. Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

CHIRAL LIGANDS USED IN TRANSITION METAL CATALYSTS FOR ASYMMETRIC ADDITION REACTIONS ESPECIALLY HYDROGENATION

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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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For a series of ferrocenyl thiophenes of type Fe(eta5-C5H4-(4-R-cC4H2S-3-yl))(eta5-C5H4-(C6H3-3,5-(CF3)2) [R = H (3a), OMe (4a)], Fe(eta5-C5H4-(4-R-cC4H2S-3-yl)(eta5-C5H4-CHO) [R = H (3b), OMe (4b)], and Fe(eta5-C5H4-(4-R-cC4H2S-3-yl)(eta5-C5H4-C?N) [R = H (3c), OMe (4c)], the influence of electron-withdrawing substituents at the ferrocenyl moiety and electron-donating groups at the thiophene unit on the electronic behavior of 3a-c and 4a-c is reported. The coupling of the ferrocenyl and the thiophene moieties has been realized using the Negishi C,C cross-coupling reaction protocol. Compounds 3a and 4c were structurally characterized by single-crystal X-ray diffraction studies. In electrochemical measurements the ferrocenyl redox potential depends on the particular substitution at the ferrocenyl and the thiophene unit. Moreover, UV/Vis/NIR studies showed ligand-to-metal charge transfer (LMCT) interactions, which occur after oxidation and are shifted bathochromically as the donor-acceptor energy gap decreases. Using different substituents, possessing electron-withdrawing or donating capabilities, allows adjusting the energy difference between the ferrocenium-acceptor unit and the donating thiophene system.

Synthesis, Properties, and Electron Transfer Studies of Ferrocenyl Thiophenes

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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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Reference of 1293-65-8, hemistry, like all the natural sciences, begins with the direct observation of nature— in this case, of matter. In a document type is Patent, molecular formula is C10Br2Fe, molecular weight is 335.76, and a compound is mentioned, 1293-65-8, 1,1′-Dibromoferrocene, introducing its new discovery.

The invention concerns a process for the manufacture of substituted propionic acids comprising providing a substrate of formula (I): And subjecting the substrate to enantioselective hydrogenation under enantioselective hydrogenation conditions in the presence of an enantioselective hydrogenation catalyst comprising a catalyst ligand having a metallocene group with a chiral phosphorus or arsenic substituent to provide in enantiomeric excess a product of formula (II): or its enantiomer or if applicable its diastereomer.

PROCESS FOR THE MANUFACTURE OF SUBSTITUTED PROPIONIC ACIDS

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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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The invention relates to a dye compound consisting of four cyclically linked components, the four components comprising at least one linker compound. According to the invention the at least one linker compound is selected from a first linker compound or a second linker compound, the first linker compound having an aromatic carboxylic acid or an alkyl ester thereof, the aromatic group being bonded to fumaronitrile, and the second linker compound having an aromatic carboxylic acid or an alkyl ester thereof, the aromatic group being bonded to phthalonitrile.

THE PREPARATION OF A DYE COMPOUND AND A METHOD FOR MAKING THE SAME

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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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Accurate computationally derived reduction potentials are important for catalyst design. In this contribution, relatively inexpensive density functional theory methods are evaluated for computing reduction potentials of a wide variety of organic, inorganic, and organometallic complexes. Astonishingly, SCRF single points on B3LYP optimized geometries with a reasonably small basis set/ECP combination works quite well–B3LYP with the BS1 [modified-LANL2DZ basis set/ECP (effective core potential) for metals, LANL2DZ(d,p) basis set/LANL2DZ ECP for heavy nonmetals (Si, P, S, Cl, and Br), and 6-31G(d’) for other elements (H, C, N, O, and F)] and implicit PCM solvation models, SMD (solvation model based on density) or IEFPCM (integral equation formalism polarizable continuum model with Bondi atomic radii and alpha = 1.1 reaction field correction factor). The IEFPCM-Bondi-B3LYP/BS1 methodology was found to be one of the least expensive and most accurate protocols, among six different density functionals tested (BP86, PBEPBE, B3LYP, B3P86, PBE0, and M06) with thirteen different basis sets (Pople split-valence basis sets, correlation consistent basis sets, or Los Alamos National Laboratory ECP/basis sets) and four solvation models (SMD, IEFPCM, IPCM, and CPCM). The MAD (mean absolute deviation) values of SCRF-B3LYP/BS1 of 49 studied species were 0.263 V for SMD and 0.233 V for IEFPCM-Bondi; and the linear correlations had respectable R2 values (R2 = 0.94 for SMD and R2 = 0.93 for IEFPCM-Bondi). These methodologies demonstrate relatively reliable, convenient, and time-saving functional/basis set/solvation model combinations in computing the reduction potentials of transition metal complexes with moderate accuracy.

Prediction of the reduction potential in transition-metal containing complexes: How expensive? For what accuracy?

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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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Reaction of l,l’,3,3′-tetra(tert-amyl)benzobis(imidazolylidene) (1) with 2 equiv of FcN3 or FcNCS afforded bisadducts [(FcN3) 2(1)] (2) or [(FcNCS)2(1)] (3), respectively (Fc = ferrocene). To the best of our knowledge, these represent the first examples of complexes comprising metals indirectly connected to the carbene atoms of N-heterocyclic carbenes (NHCs) via their ligand sets. Cyclic and differential pulse voltammetry indicated that bis(NHC) 1 facilitated significant electronic coupling between ferrocene centers in 2 (DeltaE = 140 mV), but not in 3. We believe the different degrees of electronic interaction are due to geometric factors: the triazene linker in 2 is nearly coplanar with the bis(NHC) scaffold, whereas the isothiocyanate linker is orthogonal, as determined by X-ray crystallography. Employing this “indirect connection” strategy should enable tuning of metalmetal interactions by simple alteration the organic linker between NHC and MLn fragments rather than complete redesign thereof. Given that NHC-reactive azide or isothiocyanate groups can be incorporated into both organic and inorganic compounds, this approach is envisioned to facilitate access to otherwise inaccessible catalysts and materials.

Indirectly connected bis(N-Heterocyclic Carbene) bimetallic complexes: Dependence of metal-metal electronic coupling on linker geometry

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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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A novel, unsymmetrical 1,1?-disubstituted ferrocenediyl ligand, 1-(diphenylphosphino)-1?-(methoxy)ferrocene (3), featuring phosphine and ether substituents has been synthesized via two different routes and structurally characterized. Its coordination chemistry was investigated by reaction with Rh(I), Cu(I), and group 10 metal precursors. With Ni(II) precursors, chelating complexes are formed in high yield, whereas with Pd(II) and Pt(II) precursors, either chelating complexes or monodentate bis ligand complexes with trans phosphorus ligation may be formed depending on the reaction conditions and metal precursor employed. A similar monodentate trans phosphorus-ligated complex is observed with Rh(I), whereas with Cu(I) precursors, a phosphorus-ligated monodentate bis ligand complex with a coordinated acetonitrile was obtained. Preliminary studies show that 3, in combination with either Pd(II) or Pd(0) precursors, can act as a catalyst for the Suzuki coupling reaction.

Synthesis, coordination chemistry, and catalytic application of a novel unsymmetrical P/O ferrocenediyl ligand

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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 enantioselective kinetic resolution of racemic planar-chiral metallocenylphosphine sulfides was realized by the molybdenum-catalyzed asymmetric ring-closing metathesis reaction with the krel values of up to 147. The enantiomerically enriched 1,4-but-2-enylene-bridged ferrocenylphosphine sulfides thus obtained could be purified to enantiomerically pure forms by simple recrystallization from hot methanol, and subsequent reduction of the phosphine sulfides provided the corresponding planar-chiral phosphines with retention of the enantiomeric homogeneity. This is a rare example of preparing planar-chiral ferrocenylphosphines by catalytic asymmetric reactions. The single-enantiomer planar-chiral ferrocenylphosphines were applied as chiral ligands in the rhodium-catalyzed asymmetric 1,4-addition reaction (the Hayashi-Miyaura conjugate addition reaction) of phenylboronic acid to 2-cyclohexenone to show excellent enantioselectivity and high yields. The NMR studies clarified that the butenylene-bridged ferrocenylphosphine coordinated to a rhodium(I) cation in a monodentate fashion and an interaction of the bridging olefin moiety to the rhodium atom was not detected.

Kinetic Resolution of Planar-Chiral Ferrocenylphosphine Derivatives by Molybdenum-Catalyzed Asymmetric Ring-Closing Metathesis and Their Application in Asymmetric Catalysis

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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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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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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