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Two series of asymmetric ferrocene diphosphines, namely the dppf-type ligands R2PfcPPh2 (protected as BH3 adducts; fc = ferrocene-1,1?-diyl) and their semi-homologous counterparts R2PfcCH2PPh2 (both in free and BH3-protected form), with diverse PR2 groups (R = cyclohexyl, isopropyl and tert-butyl), were prepared and further converted into the respective phosphine selenides, R2P(Se)fcP(Se)Ph2 and R2P(Se)fcCH2P(Se)Ph2, which were in turn used to evaluate the electronic properties of these diphosphines through 1JSeP coupling constants. When reacted with [PdCl2(MeCN)2] or [PdCl2(cod)] (cod = cycloocta-1,5-diene), the dppf-type ligands exclusively afforded the chelate complexes [PdCl2(R2PfcPPh2-kappa2P,P?)], whereas the more flexible, homologous ligands produced mixtures mainly containing the similar chelate complexes [PdCl2(R2PfcCH2PPh2-kappa2P,P?)] and the P,P?-bridged dimers [PdCl2(mu(P,P?)-R2PfcCH2PPh2)]2.

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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 scalable access to functionalized ferrocenyl azides has been realized in flow. By halogen-lithium exchange of ferrocenyl halides and trapping with tosyl azide, a variety of functionalized ferrocenyl azides were obtained in high yields. To allow a scalable preparation of these potentially explosive compounds, a flow protocol was developed accelerating the reaction time to minutes and circumventing accumulation of potentially hazardous intermediates. The corresponding ferrocenyl amines were then prepared by a reliable reduction process.

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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 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.

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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 iron 2p and carbon 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of substituted ferrocene compounds (Fe(Cp-(CH3) 5)2, Fe(Cp)(Cp-COOH), Fe(Cp-COOH)2, and Fe(Cp-COCH3)2) are reported and are interpreted with the aid of extended Hiickel molecular orbital (EHMO) theory and density functional theory (DFT). Significant substituent effects are observed in both the Fe 2p and C 1s NEXAFS spectra. These effects can be related to the electron donating/withdrawing properties of the cyclopentadienyl ligands and their substituents as well as the presence of pi* conjugation between the cyclopentadienyl ligand and unsaturated substituents.

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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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Abstract Compounds of the formula (I) in the form of racemates, enantiomerically pure diastereomers or a mixture of diastereomers, where the radicals R1 are identical or different and are each C1-C4-alkyl; m is 0 or an integer from 1 to 4; n is 0 or an integer from 1 to 3; p is 0 or an integer from 1 to 5; R2 is an aromatic hydrocarbon radical or a C-bonded heterohydrocarbon radical and R3 is an aliphatic or C-bonded heteroaliphatic hydrocarbon radical; R2 and R3 are identical or different and are each an aliphatic or C-bonded heteroaliphatic hydrocarbon radical; R4 is an unsubstituted or C1-C6-alkyl-, C1-C6-alkoxy- or halogen-substituted hydrocarbon radical; and A is a secondary amino group, are ligands for metal complexes which are suitable as catalysts for homogeneous enantioselective 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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Aromatic and (hetero)aromatic chromium aminocarbenes were lithiated on the (hetero)aromatic ring and transmetalated with ZnBr2. The subsequent Pd(PPh3)4- or PdCl2(XantPhos)-catalyzed Negishi reaction with dibromoarenes or chromium alkoxy-/aminocarbenes bearing bromine atoms yielded bisaminocarbene or mixed bisalkoxyaminocarbene complexes of chromium. This methodology allows easy access to the biscarbene complexes containing poly(hetero)aromatic bridges, such as biphenylene, bithienylene, tetrathienylene, 1,1?-ferrocenylene, and others. In total, 18 new biscarbene complexes, including two containing both chromium and tungsten, were synthesized in this fashion. The electrochemical behavior of the biscarbenes obtained exhibits electronic communication between the metals.

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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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Chemical engineers ensure the efficiency and safety of chemical processes, adapt the chemical make-up of products to meet environmental or economic needs, and apply new technologies to improve existing processes. Product Details of 1293-65-8. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1293-65-8, Name is 1,1′-Dibromoferrocene

The Pd-catalyzed cross-coupling reaction between halobenzenes and ferrocene-1,1′-diboronic acid is reported.Condensation proceeds smoothly to give 1,1′-diphenyl- and 1,1′-bis(halophenyl)-substituted ferrocenes bearing fluoro, chloro and bromo substituents in good yields.An effective synthesis of the intermediate ferrocene-1,1′-diboronic acid is described.

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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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These cats are purrfectionists: The ChenPhos ligands (see structure) showed dramatically higher catalytic activity in the title reaction than their C 2-symmetric predecessor with two dimethylaminoethyl-substituted ferrocenyl(phenyl)phosphanyl groups. The ready accessibility, extreme air stability, and high enantioselectivity, activity, and productivity of these ligands make them very promising for a wide range of practical applications. 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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A selective and efficient catalytic method was developed for the synthesis of new styryl-conjugated silyl-ferrocene materials. The use of an effective palladium catalytic system [Pd(eta2-dba)(P(o-tolyl)3)2] (3) with a K3PO4 base solution allowed us to obtain new, reactive ferrocene olefins which can be used in various applications. In addition, using the stereo-control silylative coupling reaction we received unique new organosilicon trans-vinylene products with a built-in metallocene.

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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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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.

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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