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The reactant in an enzyme-catalyzed reaction is called a substrate. Enzyme inhibitors cause a decrease in the reaction rate of an enzyme-catalyzed reaction. name: 1,1′-Dibromoferrocene. In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. Introducing a new discovery about 1293-65-8, Name is 1,1′-Dibromoferrocene

Ferrocenyl aryl ethers can be synthesized in good yields by Cu(I)/phosphine-catalyzed coupling reactions from iodoferrocene or 1,1?-dibromoferrocene and various phenols in toluene, using Cs2CO3 or K3PO4 as a base. For the first time a solid-state structure of a ferrocenyl-1,1?-diaryl ether [1,1?-di(4-tert-butylphenoxy)ferrocene] has been determined from single-crystal X-ray data. The mixed ferrocenyl aryl ether 1-(4-tert-butylphenoxy)-1?-(2,4-dimethylphenoxy)ferrocene was prepared in a two-step synthetic protocol.

Synthesis of ferrocenyl aryl ethers via Cu(I)/phosphine catalyst systems

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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 reactant in an enzyme-catalyzed reaction is called a substrate. Enzyme inhibitors cause a decrease in the reaction rate of an enzyme-catalyzed reaction. Formula: C10Br2Fe. In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. Introducing a new discovery about 1293-65-8, Name is 1,1′-Dibromoferrocene

Two new unsymmetrical 1?-substituted hydroxyferrocene ligands featuring either phosphine or phosphine oxide substituents have been synthesised and the phosphine oxide derivative has been structurally characterised. A nickel complex of the hydroxyl/phosphine ligand has been formed, along with preliminary evaluation of the complex for catalysis of ethylene polymerisation. The Royal Society of Chemistry 2004.

Novel unsymmetrical P/O substituted ferrocene ligands and the first structurally characterised hydroxyferrocene derivative

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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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Kinetically stabilized 1,1′-bis[(E)-diphosphenyl]ferrocenes were synthesized by taking advantage of extremely bulky substituents, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (denoted as Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (denoted as Bbt) groups, and characterized by the spectroscopic and X-ray crystallo-graphic analyses. The electronic structures of the 1,1′-bis[(E)-diphosphenyl]ferrocenes were determined by analyzing electronic spectra, the transitions of which were reasonably assigned based on theoretical calculations. In the cyclic vol-tammograms, there were two well-defined reversible one-electron reduction couples corresponding to the intramolecular two diphosphene units. Furthermore, the 1,1′-bis[(E)-diphosphenyl]ferrocene was found to undergo ligand-exchange reactions with group 6 metal carbonyl complexes along with the E-to-Z isomerization of the diphosphene moieties, leading to the formation of the corresponding 1,1′-bis[(Z)-diphosphenyl]ferrocene group 6 metal tetracarbonyl complexes, [M(CO) 4{(Z,Z)-(BbtP=PC 5H4)2Fe}] (M = Cr, Mo, and W). The molecular structures of these complexes were determined by spectroscopic analyses ( 1H, 13C, and 31PNMR spectra, and UV-vis spectra), and that of the tungsten complex was determined by X-ray crystallographic analysis. Several types of d? pi*p=p electron transitions due to the iron and group 6 metals were detected by using UV-vis spectroscopy, and these results were supported by theoretical calculations.

Kinetically stabilized 1,1′-bis[(E)-dipnosphenyl]ferrocenes: syntheses, structures, properties, and reactivity

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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 synthesis of a series of ferrocenylanthracene derivatives is described, utilising the palladium catalysed coupling reaction of 1,1?-bis(chlorozincio)ferrocene with halo-anthracenes. Bis-1,1?-(9-anthracenyl)ferrocene (1) was characterised by single crystal X-ray diffraction and shows an eclipsed ferrocenyl geometry. X-ray crystallographic studies indicate that there are no clear stacking interactions of either an intra-or intermolecular nature between the anthracenyl rings in the structure. A series of 9-and 10-disubstituted ferrocenylanthracene derivatives has also been prepared. In each case the palladium catalyst (Pd(dppf)Cl2) is recovered in a modified form, e.g. as the [(dppf)PdBr(9-anthracenyl)] complex in the synthesis of bis-1,1?-(9-anthracenyl)ferrocene. The single crystal X-ray structure of one such palladium complex [(dppf)PdBr-{9-(10-chloroanthracenyl)}] (15a) has been determined in a case where chloride/bromide exchange had occurred in the palladium complex intermediate. The potential application of compound 1 as synthon for the construction of a molecular sensing device is discussed. Cyclic voltammetry and fluorescence studies have been carried out for selected derivatives.

Ferrocenyl anthracenes: Synthesis and molecular structure

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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 synthesis and mercuration of a series of Schiff bases 1?-benzoyl-1-[(arylimino)phenylmethyl]ferrocene (aryl: a variety of substituted phenyls) have been studied. In all cases the mercuration occurred at the 2-position of the ferrocene ring. Oxygen ? mercury coordinated products were not obtained. The X-ray crystal structure of [2-chloromercurio-1-[((phenylimino)phenylmethyl)-1?-benzoyl] ferrocene 5c has been determined; this crystallizes in the monoclinic, space group P21/c with a =10.168(3), b= 16.105(3), c = 15,463(4)A, beta = 103.61(2) and Z = 4. Refinement of atomic parameters gave an R factor of 0.038 (Romega = 0.055) for 2440 unique reflections having 1>3sigma(1). The structure confirms the formation of a five-membered metallocycle on the ferrocene moiety.

Cyclometallation of ferrocenylimines III. Regioselectivity in Hg(II) cyclometallated 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

 

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Palladium(II) and nickel(II) halide complexes of the ferrocenyl polyphosphines 1,1?,2,3-tetrakis(diphenylphosphino)ferrocene (1), and 1,1?,2-tris(diphenylphosphino)-4-tert-butylferrocene (5) were prepared and characterized by multinuclear NMR. The metallo-ligand 1, the palladium [Pd 2Cl4(1)] (3b) and nickel [NiCl2(5)] (6) coordination complexes were additionally characterized by X-ray diffraction crystallography. The behavior of 1 toward coordination to nickel and palladium was surprisingly different because the coordination of a second metal center after the initial 1,2-phosphorus-bonding of nickel was markedly difficult. The preference of nickel for 1,2-P coordination on 1,1?-bonding was confirmed by the exclusive formation of 6 from 5. The changes noted between the solid state structure of the ligand 1 and the structure obtained for the dinuclear palladium complex 3b reveal the rotational flexibility of this tetraphosphine. This flexibility is at the origin of the unique framework for a metallocenic dinuclear metal complex in which both coexist a 1,1?-heteroannular chelating P-bonding and a 2,3-homoannular chelating P-bonding with two palladium centers. Some reported specimens of ferrocenyl polyphosphines of constrained geometry have previously revealed that phosphorus lone pair overlap can lead to very intense “through-space” 31P31P nuclear spin-spin coupling constants (JPP) (J. Am. Chem. Soc. 2004, 126 (35), 11077-11087] in solution phase. In these cases, an intemuclear distance between heteroannular phosphorus atoms below 4.9 A, with an adequate orientation of the lone-pairs in the solid state and in solution, was a necessary parameter. The flexibility of the new polyphosphines 1 and 5 does not allow that spatial proximity (intemuclear distances between heteroannular phosphorus above 5.2 A in the solid state); accordingly the expected through-space nuclear spin-spin coupling constants were not detected in any of their coordination complexes nor in 1.

Coordination chemistry of tetra- and tridentate ferrocenyl polyphosphines: An unprecedented [1,1?-heteroannular and 2,3-homoannular]-phosphorus- bonding framework in a metallocene dinuclear coordination complex

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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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To determine the trans effect on the rates of reductive eliminations from arylpalladium(II) amido complexes, the reactions of arylpalladium amido complexes bearing symmetrical and unsymmetrical DPPF (DPPF = bis(diphenylphosphino)ferrocene) derivatives were studied. THF solutions of LPd(Ar)(NMeAr?) (L = DPPF, DPPF-OMe, DPPF-CF3, DPPF-OMe,Ph, DPPF-Ph,CF3, and DPPF-OMe,CF3; Ar = C6H 4-4-CF3; Ar? = C6H4-4-CH 3, Ph, and C6H4-4-OMe) underwent C-N bond forming reductive elimination at -15 C to form the corresponding N-methyldiarylamine in high yield. Complexes ligated by symmetrical DPPF derivatives with electron-withdrawing substituents on the DPPF aryl groups underwent reductive elimination faster than complexes ligated by symmetrical DPPF derivatives with electron-donating substituents on the ligand aryl groups. Studies of arylpalladium amido complexes containing unsymmetrical DPPF ligands revealed several trends. First, the complex with the weaker donor trans to nitrogen and the stronger donor trans to the palladium-bound aryl group underwent reductive elimination faster than the regioisomeric complex with the stronger donor trans to nitrogen and the weaker donor trans to the palladium-bound aryl group. Second, the effect of varying the substituents on the phosphorus donor trans to the nitrogen was larger than the effect of varying the substituents on the phosphorus donor trans to the palladium-bound aryl group. Third, the difference in rate between the isomeric arylpalladium amido complexes was similar in magnitude to the differences in rates resulting from conventional variation of substituents on the symmetric phosphine ligands. This result suggests that the geometry of the complex is equal in importance to the donating ability of the dative ligands. The ratio of the differences in rates of reaction of the isomeric complexes was similar to the relative populations of the two geometric isomers. This result and consideration of transition state geometries suggest that the reaction rates are controlled more by substituent effects on ground state stability than on transition state energies. In addition, variation of the aryl group at the amido nitrogen showed systematically that complexes with more electron-donating groups at nitrogen undergo faster reductive elimination than those with less electron-donating groups at nitrogen.

Trans Influence on the Rate of Reductive Elimination. Reductive Elimination of Amines from Isomeric Arylpalladium Amides with Unsymmetrical Coordination Spheres

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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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Palladium catalyzed Negishi, Suzuki and Stille cross-coupling reactions of enantiopure 2,2?-diiodo-1,1?-binaphthyl with the corresponding 1,1?-dimetalloferrocenes gave the C2-symmetric binaphthyl bridged ferrocene 1-1,1?-(1,1?-binaphthyl-2,2?-diyl)ferrocene (1). The latter was obtained by Stille coupling with the bis(trimethylstannyl) derivative but not with the bis(tributylstannyl) one. Products of alkyl group transfer from tin to binaphthyl were obtained as the main products in both cases. The stereochemical result of these cross-coupling reactions in the positions 2 and 2? of 1,1?-binaphthyl depends on the reactivity of 1,1?-dimetalloferrocenes. Negishi coupling proceeds stereoconservatively (affording enantiopure product 1). Complete racemization of binaphthyl moiety occurs during the reactions with less reactive boron and tin organometallics. Proposed different reaction pathways include C1-symmetric palladium(II) intermediate in the former and configurationally unstable C2-symmetric pallada(IV)cyclic intermediate in the latter cases. In contrast to the cross-coupling reactions, free radical arylation of ferrocene with enantiopure 1,1?-binaphthyl-2,2?-bisdiazonium salt gave predominantly oligomeric binaphthyl bridged ferrocenes and only traces of the partially racemized product 1.

Study on the synthesis of nonracemic C2-symmetric 1,1?-binaphthyl-2,2?-diyl bridged ferrocene. Stereochemical result of the cross-coupling reactions controlled by Pd(II) or Pd(IV) complex intermediacy

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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 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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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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We report the synthesis and full characterization of the entire haloferrocene (FcX) and 1,1?-dihaloferrocene (fcX2) series (X = I, Br, Cl, F; Fc = ferrocenyl, fc = ferrocene-1,1?-diyl). Finalization of this simple, yet intriguing set of compounds has been delayed by synthetic challenges associated with the incorporation of fluorine substituents. Successful preparation of fluoroferrocene (FcF) and 1,1?-difluoroferrocene (fcF2) were ultimately achieved using reactions between the appropriate lithiated ferrocene species and N-fluorobenzenesulfonimide (NFSI). The crude reaction products, in addition to those resulting from analogous preparations of chloroferrocene (FcCl) and 1,1?-dichloroferrocene (fcCl2), were utilized as model systems to probe the limits of a previously reported “oxidative purification” methodology. From this investigation and careful solution voltammetry studies, we find that the fluorinated derivatives exhibit the lowest redox potentials of each of the FcX and fcX2 series. This counterintuitive result is discussed with reference to the spectroscopic, structural, and first-principles calculations of these and related materials.

The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

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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