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Compounds of the formula I in the form of enantiomerically pure diastereomers or a mixture of diastereomers, (I), where the radicals R1 are identical or different and are each C1-C4-alkyl; m is 0 or an integer from 1 to 3; n is 0 or an integer from 1 to 4; R2 is a hydrocarbon radical or a C-bonded heterohydrocarbon radical; Cp is unsubstituted or C1-C4-alkyl-substituted cyclopentadienyl; Y is a C-bonded chiral group which directs metals of metallation reagents into the ortho position; and Phos is a P-bonded P(III) substituent. The compounds are chiral ligands for complexes of transition metals which are used as homogeneous catalysts in asymmetric syntheses.

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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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Compounds of the formula I in the form of enantiomerically pure diastereomers or a mixture of diastereomers, (I), where the radicals R1 are identical or different and are each C1-C4-alkyl; m is 0 or an integer from 1 to 3; n is 0 or an integer from 1 to 4; R2 is a hydrocarbon radical or a C-bonded heterohydrocarbon radical; Cp is unsubstituted or C1-C4-alkyl-substituted cyclopentadienyl; Y is a C-bonded chiral group which directs metals of metallation reagents into the ortho position; and Phos is a P-bonded P(III) substituent. The compounds are chiral ligands for complexes of transition metals which are used as homogeneous catalysts in asymmetric syntheses.

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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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Novel bidentate ligands of general formula (I) are described Formula (I): R represents a hydrocarbyl aromatic structure. The substituent(s) Yx on the aromatic structure has a total X=1-n SigmatYx of atoms other than hydrogen such that x-1-nSigmatYx is ? 4, where n is the total number of substituent(s) Yx and tYx represents the total number of atoms other than hydrogen on a particular substituent Yx. The groups X1, X2, X3 and X4 are joined to Q1 or Q2 via tertiary carbon atoms to the respective atom Q1 or Q2; and Q1 and Q2 each independently represent phosphorus, arsenic or antimony. A catalyst system and a process for the carbonylation of ethylenically unsaturated compounds utilising the catalyst system is also described.

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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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Convenient new methods are developed for the preparation of 1?,1??-disubstituted triferrocenes and tetraferrocenes that can be oxidized with iodine to a new series of mixed-valence compounds. The X-ray structures of 1?,1??-diethyltriferrocene, 1?,1??-dimethoxymethyltriferrocene, and 1?,1??-dimethoxymethyltetraferrocene have been determined at 298 K. The rates of intramolecular electron transfer in these mixed-valence cations were estimated by variable-temperature 57Fe Moessbauer experiments. The features in all 80 and 300 K spectra include two doublets, one with a quadrupole splitting (DeltaEQ) of ?2 mm s-1 (Fe(II) site) and the other with DeltaEQ = ?0.3 mm s-1 (Fe(III) site). This pattern of two doublets is expected for a mixed-valence biferrocenium cation that is valence-trapped on the time scale of the Moessbauer technique (electron-transfer rate COA of Formula: C10Br2Fe

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 polysaccharide-based chiral stationary phase (CSP) columns, Daicel Chiralpak IA, IB, and IC, were applied in the separation of the nonenantiomeric isomers of various organometallic compounds and were found to be highly effective in recognizing isomers of minor structural differences. The CSP columns have succeeded to separate the double-bond regioisomers in bridged (eta5-formylcyclopentadienyl)manganese(I) dicarbonyl complexes 1a/1b, the structural isomers of methylbutenylferrocene derivatives in 2a/2b and 3a/3b, and the geometrical isomers of the (2-methyl-2-butenyl)ferrocenes in (Z)/(E)-3b. Due to the close similarity of the isomeric compounds in these mixtures, separations of the components are extremely difficult and could not be attained by conventional methods such as silica gel column chromatography, silica gel HPLC, recrystallization, distillation/sublimation, etc. Clearly, the polysaccharide-based CSP columns have unique advantages in separation/purification technology, and this study has shown potential usefulness of the CSP columns in separation of not only enantiomeric but also nonenantiomeric mixtures.

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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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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.

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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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Three [2]ferrocenophanes ([2]FCPs) bridged by nitrogen and silicon (7SiMe2) and nitrogen and tin (7SnMe2, 7SntBu2) were synthesized by salt metathesis between a dilithioferrocene derivative, prepared in situ from 1-bromo-1?-(trimethylsilylamino)ferrocene (6), and Me2SiCl2, Me2SnCl2, and tBu2SnCl2, respectively. A multistep synthesis of precursor 6 is described. Only 7SiMe2 and 7SntBu2 could be prepared as analytically pure compounds. The molecular structures of all three [2]FCPs were determined by single-crystal X-ray analysis. Expectedly, the tilting of the Cp ligands in the silicon species 7SiMe2 is larger [alpha = 15.73(13)] than in the tin compounds 7SnMe2 [alpha = 9.36(17) and 9.45(18)] and 7SntBu2 [alpha = 10.13(11)]. Ring-opening polymerizations of 7SiMe2 and 7SntBu2 were attempted using the common methods of thermal, transition-metal-catalyzed, anionic, and photocontrolled ring-opening polymerization, but none of the experiments gave polymeric materials. (Figure Presented).

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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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Deuterium exchange of certain substituted ferrocenes (under very mild basic conditions) occurs in only the substituted cyclopentadienyl-ring in non-statistical pattern; a ?->? (eta5->eta1) rearrangement mechanism is proposed to account for the novel pattern of exchange.

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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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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+.

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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 syntheses and structural characterization of sterically encumbered 1,2-diborylferrocenes are reported, together with an investigation of their anion recognition capabilities with respect to fluoride and cyanide. Surprisingly, 1,2-fc(BMes2)2 is found to be highly selective for CN-, with the uptake of F- being shown to be not only thermodynamically less favorable but also kinetically much slower.

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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