Archives for Chemistry Experiments of 1,1′-Dibromoferrocene

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Ir-catalyzed C-H activation in the synthesis of borylated ferrocenes and half sandwich compounds

The complex generated from 1/2 [Ir(OMe)(cod)]2 and 4,4?-di-tert-butyl-2,2?-bipyridine catalyzes the regioselective borylation of ferrocenes, CpMn(CO)3 and CpMo(CO)3CH 3 with a stoichiometric amount of B2pin2.

Ir-catalyzed C-H activation in the synthesis of borylated ferrocenes and half sandwich compounds

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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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Acyl-substituted ferrocenes as driers for solvent-borne alkyd paints

Ferrocenes bearing acyl substituents in the cyclopentadienyl rings [Fe(eta5-C5H4COR)(eta5-C 5H5)] and [Fe(eta5-C5H 4COR)2] (R = CH3, CF3 and Ph) were examined as new driers for solvent-borne alkyd binder. All studied ferrocenes were found to be active catalysts for cross-linking reaction of the alkyd. These iron(II) compounds give solid polymeric films with hardness and drying time comparable to the commercial cobalt(II) drier. Acetyl- and benzoyl-substituted ferrocenes show an excellent synergic effect with the cobalt drier giving hard polymeric films within short drying time. The kinetics of the alkyd autoxidation was followed by FTIR spectroscopy. Spin-trapping ESR technique has proven the important role of the ferrocenium cation upon decomposition of hydroperoxides by ferrocene-based driers. The peroxy and alkoxy radicals, appearing in drying process, were resolved by the new spin trap methyl-N-mesityl nitrone.

Acyl-substituted ferrocenes as driers for solvent-borne alkyd paints

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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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Comparison of doubly lithiated, magnesiated, and zincated ferrocenes: [Fe(eta5-C5H4)2] 2Zn2(tmeda)2, the first example of a [1.1]ferrocenophane with bridging first-row transition metal atoms

Starting from doubly lithiated ferrocene [Fe(eta5-C 5H4)2]3Li6(tmeda) 2 (1), the corresponding thf adduct [Fe(eta5-C 5H4)2]2Li4(thf) 6 (3) was prepared by recrystallization of 1 from thf. In contrast to 1, which features six Li+ cations surrounded by 1,1?- ferrocenediyl fragments in a carousel arrangement, compound 3 contains only two ferrocenediyl anions bridged by four Li+ cations. This comparison clearly reveals the strong impact of different supporting ligands on the solid-state structures of lithiated ferrocenes. The doubly magnesiated and zincated derivatives [Fe(eta-C5H4) (tmeda)2 (4) and [Fe(eta5-C5H4)2] 2Zn2(tmeda)2 (6) were synthesized via salt metathesis using 1 and MgCl2 or ZnCl2, respectively. Even though Mg2+ and Zn2+ are chemically related ions, the solid-state structures of 4 and 6 turned out to be distinctly different. Compound 4 possesses a cluster structure reminiscent of the lithiated aggregate 1, whereas 6 represents the first example of a first-row transition metal-bridged [1.1]-ferrocenophane (anri-conformation). All three doubly metallated ferrocenes 3, 4, and 6 are suitable reagents for the preparation of 1,1?-disubstituted ferrocenes as has been exemplified for the synthesis of Fe(eta5-C5H4SiMe3)2 (5). We have also shown that 5 can be generated in yields exceeding 90% from Fe(eta;5-C5H4Br)2, Me 3SiCl, and Rieke magnesium.

Comparison of doubly lithiated, magnesiated, and zincated ferrocenes: [Fe(eta5-C5H4)2] 2Zn2(tmeda)2, the first example of a [1.1]ferrocenophane with bridging first-row transition metal atoms

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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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Phosphorus-chiral diphosphines as ligands in hydroformylation. An investigation on the influence of electronic effects in catalysis

The phosphorus-chiral diphosphine 1,1?-bis(1-naphthylphenylphosphino)ferrocene (1a) and its new electronically modified derivatives 1b-d bearing methoxy and/or trifluoromethyl groups in para positions of the phenyl rings were investigated as ligands in rhodium-catalyzed (asymmetric) hydroformylation. Depending on ligand basicity, high-pressure NMR and IR characterization of the respective (diphosphine) rhodium dicarbonyl hydride precursor complexes revealed subtle differences in the occupation of bis-equatorial (ee) and equatorialapical (ea) coordination geometries. The high ee:ea ratio of the four complexes contrasted with the clear ea preference observed for the related achiral compound dppf (1,1?-bis-(diphenylphosphino)ferrocene). In the hydroformylation of styrene the best result (50% ee) was obtained by employing the best pi-acceptor ligand 1c, incorporating two p-trifluoromethyl substituents. Substrate electronic variations using 4-methoxystyrene and 4-chlorostyrene showed a pronounced influence on turnover frequencies, branched/linear aldehyde product ratios, and enantiodiscrimation, whereas in the hydroformylation of 1-octene ligand electronic perturbations did affect only the rate, but not the selectivity of the reaction.

Phosphorus-chiral diphosphines as ligands in hydroformylation. An investigation on the influence of electronic effects in 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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Enantioselective reduction of benzoyl derivatives of ferrocene and ruthenocene: optically active carbinols and carbenium ions

Mono- and 1,1′-disubstituted metallocenes, XC5H4MC5H4Y, M = Fe, Ru, X = H, Y = COPh, or X = Y = COPh, have been reduced using the LiAlH4-Chirald complex to afford the corresponding carbinols and diols enantiomerically enriched.Optical yield was 53percent for benzoylferrocene and 86percent for benzoylruthenocene, (R)-configuration being predominant.Monocations had an opposite sign of rotation and were stable in CF3COOH.On the contrary, diols have lost optical rotation in the same acid that has been explained by formation of the achiral ether intermediate.Dication has been formed in DSO3F as evidenced by the 1H NMR spectrum but it is completely racemized even at low temperature.

Enantioselective reduction of benzoyl derivatives of ferrocene and ruthenocene: optically active carbinols and carbenium ions

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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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Simple Synthesis and Chemicophysical Properties of Polyoxaferrocenophanes and Its Alkali Metal Complexes

Polyoxaferrocenophanes were synthesized by a one-pot reaction of 1,1′-diacetoxyferrocene with dichloride.Crystalline 1 : 1 complexes of 3a with LiSCN, NaSCN, and KSCN were isolated.The 1H-NMR and Moessbauer spectra of these complexes suggest the possibility of a certain interaction between the iron atom of the ferrocene nuclei and complexed cation.The new type of ferrocenophane 3a extracts thallium ion most effectively, the extractability of several metal ions being in this order; Tl+ > Rb+ > K+ > Cs+ > Na+.

Simple Synthesis and Chemicophysical Properties of Polyoxaferrocenophanes and Its Alkali Metal Complexes

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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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COMPARISON OF THE ELECTRONIC STRUCTURE OF DISUBSTITUTED FERROCENES.

We have measured the optical absorption of gaseous ferrocene, 1,1 prime -dimethylferrocene, 1,1 prime -dibromoferrocene, and 1,1 prime -dichloroferrocene using synchrotron radiation. From these data we have estimated the ligand field parameters and noted increasing e//2//g(d) to Cp( pi ) overlap with increasing charge transfer from the Cp ring to the substitution. The optical absorption spectra for ferrocene, dibromoferrocene, and dichloroferrocene are remarkably similar. The halogen substitutions result in greater Cp( pi ) to e//2//g-(d(x2-y2)) hybridization. The e//2//g orbitals become more bonding while the a//1//g and e//1//g orbitals become more non-bonding or antibonding. This change is reflected in a change of the ligand field parameters.

COMPARISON OF THE ELECTRONIC STRUCTURE OF DISUBSTITUTED FERROCENES.

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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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Synthesis and some Propeties of ferrocene Derivatives having a Long Alkyl Chain. Formation of a Regularly oriented Organometallic Complex in Monolayer Assemblies

1′,6′-Bis(stearoyloxy)biferrocene was synthesized and its Langmuir-Blodgett film was prepared, in which film the cyclopentadienyl rings of a ferrocene nucleus were orientated perpendicular to the film surface.Oxiadtion of the biferrocene derivative gave the mixed velence monocation complex which formed a stable monolayer on water.

Synthesis and some Propeties of ferrocene Derivatives having a Long Alkyl Chain. Formation of a Regularly oriented Organometallic Complex in Monolayer Assemblies

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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

 

Archives for Chemistry Experiments of 1,1′-Dibenzoylferrocene

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Ferrocene-containing acetylenic peroxy alcohols

Lithium tert-alkylperoxyacetylides were reacted with acetyl-, benzoyl, and 1,1?-dibenzoylferrocenes to obtain previously unknown ferrocene-containing acetylenic mono- and diperoxy alcohols. Thermal stability of the products was evaluated.

Ferrocene-containing acetylenic peroxy alcohols

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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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Ferrocenyl-substituted bicyclo[1.1.1]pentasilanes: Evaluation of significant interactions between ferrocenyl units and rigid silicon cages

Ferrocenyl-substituted bicyclo[1.1.1]pentasilanes 1, 2, and 3 were synthesized by the reactions of bromo-substituted bicyclo[1.1.1]pentasilanes with lithioferrocene. Significant interactions between bicyclo[1.1.1]pentasilane and ferrocenyl units were suggested by cyclic voltammetry, UVvis absorption spectrum, and theoretical calculations.

Ferrocenyl-substituted bicyclo[1.1.1]pentasilanes: Evaluation of significant interactions between ferrocenyl units and rigid silicon cages

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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