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New multisite ligands containing either three peripherally linked ferrocene redox centres (L1,L3) or three externally orientated 2,2′-bipyridyl transition metal recognition sites (L2,L4) have been prepared and their homo- and hetero-polymetallic zinc(II) and copper(I) cryptates incorporating in the case of L2 and L4 externally coordinated ruthenium(II) cations have been isolated.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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A short and efficient preparation of conjugated oligo(phenylene-ethylene) thiols bearing redox-active ferrocene moieties is described. While minimising the number of synthetic steps, the proposed strategy permits the development of sets of oligomers with varying chain length. The redox properties of the compounds in solution are determined. Preliminary studies of self-assembled monolayers (SAMs) on gold electrodes are discussed, and indicate that electron transfer through the SAMs is indeed rapid. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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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 synthesis, X-ray structure and magnetic properties of two new ferrocene substituted nitroxide monoradicals are described. The magnetic susceptibility data was nicely fitted in both cases to the Curie-Weiss law yielding the Weiss constants of theta=-1.8 and -1.1 K for radicals 1 and 2, respectively. This result evidenced the presence of very weak antiferromagnetic intermolecular interactions between neighbor molecules. Moreover, the X-ray structure of the key precursor 2,3-bis(hydroxyamino-)-2,3-dimethylbutane (3) is also included.

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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 of ferrocene- and ruthenocene-functionalized tetraazamacrocyclic ligands and their corresponding transition metal complexes are described. Reaction of N,N?-bis(2-aminoethyl)-1,3-propanediamine (2,3,2-tet) with 1,1?-diformylferrocene and 1,1?-diformylruthenocene produces the ligands fcmac and rcmac in 81-85% yield. Examination of their CuII, NiII, CoII, ZnII and Fe II/III complexes by IR, UV/Vis, EPR and Moessbauer spectroscopy as well as by electrochemical studies suggests electronic communication between the two metal centers of each complex. The molecular structure of [Cu II(fcmac)(FBF3)]BF4, determined by X-ray structure analysis, is reported and shows that the distance between the two metals is 4.54 A. Stability constants, determined by potentiometric titration, indicate that the copper(II) complexes are of similar stability as those with unfunctionalized tetraazamacrocyclic ligands (e.g. cyclam = 1,4,8,11-tetraazacyclotetradecane); stability constants of cobalt(II) complexes are about 2 log units smaller, those of nickel(II) and zinc(II) complexes are reduced by more than 10 log units. This selectivity is discussed on the basis of the structural studies. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

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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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Herein is described the synthesis of (+)-camphor derivatives containing sulfonamide groups, ferrocenylmethylidene or arylidene moieties. The obtained derivatives were tested against seven human cancer cells lines, namely BV-173, K-256a, NB-4, A549, H1299, MCF-7, and MDA-MB231, and two normal human cell lines, HEK293 and HUVEC, in order to determine their activity against malignant cells. Some of them exhibit IC50 values below 10 muM in at least one of the cancer cell lines. Ferrocenylmethylidene ketone 16 can be outlined as the most potent and selective in the current study (IC50 for cancer cells-up to 4.0 muM; IC50 for HEK293 and HUVEC-68 and 69 muM, respectively). There is a clear trend showing that the presence of a conjugated ferrocenylmethylidene group is essential for the cytotoxicity, however different sulfonamide substituents and derivatization of the carbonyl group can modify the activity. Thus, this class of compounds could have good prospects for further structural optimisation.

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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 chiral modular C2-symmetric ferrocenyl phosphinite ligands have been synthesized in good yields by using 1,1?-ferrocenedicarboxyaldehyde and various amino alcohols as starting materials, and applied in the iridium(III)-catalyzed asymmetric transfer hydrogenations of aromatic ketones to give the corresponding secondary alcohols with good enantioselectivities and reactivities using 2-propanol as the hydrogen source (up to 98% ee and 99% conversion). The substituents on the backbone of the ligands were found to have a significant effect on both the activity and enantiomeric excess. The structures of these complexes have been clarified by a combination of multinuclear NMR spectroscopy, IR spectroscopy, and elemental analysis.

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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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From the reaction of [PtCl2(N-CMe)2] with FcC-N (1) (Fc = Fe(eta5-C5H4)(eta5-C 5H5)) complex [PtCl2(FcC-N)(N-CMe)] (2) was obtained, which on subsequent treatment with 1 gave trans-[PtCl 2(N-CFc)2] (trans-3). The latter complex and the appropriate cis isomer (cis-3) were also accessible when [PtCl2] or [PtCl2(N-CMe)2] is reacted with a 2.6-fold excess of 1. Appropriate treatment of [PtCl2(N-CMe)2] with two equivalents of 1-acetyl-1′-cyanoferrocene (4) produced trans-[PtCl 2(Fe(eta5-C5H4CN)( eta5-C5H4C(O)Me))2] (trans-5). Coordination polymer [PtCl2(Fe(eta5-C5H 4CN)2)]n (7) was obtained by combining [PtCl2(N-CPh)2] with [Fe(eta5-C 5H4CN)2] (6). However, when 7 was reacted with PPh3 for deaggregation, [PtCl2(PPh3) 2] was formed. Addition of FcC-CLi (8-Li) to trans-3 gave pentametallic trans-[Pt(C-CFc)2(NH-CnBuFc)2] (10) via trans-[Pt(C-CFc)2(N-CFc)2] (9). When trans-3 is reacted with two equivalents of nBuLi in the absence of FcC-CH (8), trans-[PtCl2(NH-CnBuFc)2] (11) was obtained, which decomposed to FcC(-NH)nBu (12), giving FcC(O)nBu (13). Electrochemical measurements of the nitrile platinum complexes show no redox separation for the oxidation of the Fc and Fe(eta5-C 5H4)2 moieties. Compared with the noncoordinated ferrocenecarbonitriles, a shift to higher potentials is observed. In contrast, for 10 four well-separated redox events (-185, -90, +460, +545 mV) were found, which could be assigned to the oxidation of the Fc units. UV-vis/NIR spectroscopy allowed to determine an IVCT absorption (numax = 6495 cm-1, epsilonmax = 270 L·mol-1·cm-1, Deltanu1/2 = 2270 cm-1) for 10+, classifying this mixed-valent species as a weakly coupled class II system according to Robin and Day, while no IVCT transitions were observed for 10n+ (n = 2, 3). The structures of trans-3, cis-3, 10, and FcC(O)tBu (15) in the solid state were determined by single-crystal X-ray diffraction. Although the bond distances and angles of trans-3 and cis-3 are similar, the cis isomer crystallizes as a dimer possessing Pt-Pt distances within the sum of the van der Waals radii.

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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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In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts are in the same phase as the reactants. COA of Formula: C12H10FeO2. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1271-48-3, Name is 1,1′-Ferrocenedicarboxaldehyde

Planar chiral phosphines displaying a new ferrocenophane scaffold have been prepared via a stereoselective approach. The P-cyclohexyl substituted phosphine affords high levels of asymmetric induction in the organocatalytic [3 + 2] annulation reaction between allenes and electron-poor olefins. Copyright

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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 potential use of (aminomethyl)ferrocene and 1,1? -di(aminomethyl)ferrocene as precursor for Schiff base chemistry has been tested. (Aminomethyl)ferrocene reacts with 3,3? -(3-oxapentane-1,5-diyldioxy)bis(2-hydroxybenzaldehyde) to give the [2+1] diiminic ligand 8. 8 reacts with LaCl3 and Ni(CH3COO) 2 giving the corresponding complexes 9 and 10. 1,1? -Di(aminomethyl)ferrocene was prepared by conversion of 1,1? -di(formyl)ferrocene into 1,1?-di(formyl)ferrocene oxime, followed by reduction of the oxime with LiAlH4. Easy degradation of 1,1?-di(aminomethyl)ferrocene prevented its use as aminic precursor for the synthesis of Schiff base ligands. Isomerization occurred about the carbon-nitrogen double bonds of 1,1?-di(formyl)ferrocene oxime giving rise to three isomers. The X-ray analysis has shown that in the 5a complex three independent molecules having different conformation are present.

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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 first sumanene-ferrocene probes for efficient and selective caesium cation (Cs+) recognition are reported. The working mechanism of the sumanene moiety as the sensing unit was based on the site-selective cation-pi interaction in its neutral state. The interactions with Cs+ were characterized by high association constant values together with low limits of detection.

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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