1273-76-3Relevant academic research and scientific papers
Oligomerization of phenylferrocenylacetylene under the action of WCl 6
Tatarinova, Inna V.,Tarasova, Ol'Ga A.,Markova, Marina V.,Morozova, Lyudmila V.,Mikhaleva, Al'Bina I.,Trofimov, Boris A.
, p. 124 - 127 (2012)
Phenylferrocenylacetylene was found to be capable of oligomerizing in the presence of WCl6 (130 °C, 24 h) to afford short polyenes (with about 5 monomer units in the macromolecule) in up to ～30% yield. The polyenes synthesized are promising rea
The syntheses and electrochemical studies of a ferrocene substituted diiminopyridine ligand and its P, S, Se, and Te complexes
Magdzinski, Eleanor,Gobbo, Pierangelo,Martin, Caleb D.,Workentin, Mark S.,Ragogna, Paul J.
, p. 8425 - 8432 (2012)
A new reversible, redox active diiminopyridine ligand (1Fc) containing pendant ferrocene functionalities was isolated and fully characterized. The reaction of 1Fc with chalcogen pseudohalides of sulfur, selenium, and tellurium yielded the respective N,N′,N″-chelated chalcogen dications. Phosphorus chemistry proceeded in a related manner but, in this case, by the direct addition of 1Fc with PI3 to yield the N,N′,N″- chelated P(I) cation. These species represent the first synthesized main group complexes involving a redox active diiminopyridine ligand containing pendant ferrocenes. Electrochemical studies of the free ligand shows a reversible two-electron process. The chelated phosphorus cation, however, displayed three events, the first being a quasi-reversible two-electron process, involving the oxidation at the P(I) center, resulting in a P(III) cation. The subsequent reversible one- and two-electron processes arise from the ligand framework and pendant ferrocenes, respectively.
Facile purification of iodoferrocene
Goeltz, John C.,Kubiak, Clifford P.
, p. 3908 - 3910 (2011)
We report a simple method for purifying large amounts of iodoferrocene, synthesized in one step from ferrocene. Halogenated ferrocene derivatives have been known for some time, but are commonly not purified, as obtaining pure samples typically requires multiple steps and often involves use of highly toxic organomercury complexes. The purification described here takes advantage of the increased oxidation potential of iodoferrocene, relative to ferrocene.
Synthesis of ferrocene amides and esters from aminoferrocene and 2-substituted ferrocenecarboxylic acid and properties thereof
Srinivas, Palabindela,Prabhakar, Sunchu,Chevallier, Floris,Nassar, Ekhlass,Erb, William,Dorcet, Vincent,Jouikov, Viatcheslav,Radha Krishna, Palakodety,Mongin, Florence
, p. 9441 - 9447 (2016)
Different ferrocenecarboxamides were synthesized from aminoferrocene and various acid coupling partners such as Nα-Boc-l-tryptophan and N-protected sugar amino acids (N-Boc-3-amino-3-deoxy-1,2-O-isopropylidene-α-d-ribofuranoic acid, N-Boc-3-amino-3-deoxy-1,2-O-isopropylidene-α-d-xylofuranoic acid and their corresponding homo- and hetero-dimers). Similarly, reactions between 2-aminoethyl ferrocenecarboxylate and N-protected sugar amino acids afforded compounds with a carboxamide functional group remotely positioned from the ferrocene core. The X-ray diffraction structure of one of them showed the presence of an intermolecular hydrogen bond between the amide functional groups. Carbonylamino (or carbonyloxy) and oxycarbonyl 1,2-disubstituted ferrocenes were prepared either as racemic mixtures or in enantiomerically pure (SP) form. Their electrochemical evaluation revealed distinctive features. Interestingly, the enantiomerically pure ferrocene diester showed a large potential shift (+45 mV) in the presence of l-glutamic acid. Finally, some of the synthesized ferrocenes were evaluated for their antibacterial, antifungal and antiproliferative (MCF-7) activities.
Enantioselective Twofold C?H Annulation of Formamides and Alkynes without Built-in Chelating Groups
Chen, Hao,Luan, Yu-Xin,Wang, Yin-Xia,Ye, Mengchun
, p. 9428 - 9432 (2020)
Twofold C?H annulation of readily available formamides and alkynes without built-in chelating groups was achieved. Ni?Al bimetallic catalysis enabled by a bulky BINOL-derived chiral secondary phosphine oxide (SPO) ligand proved to be critical for high reactivity and high selectivity. This reaction uses readily available formamides as starting materials and provides a concise synthetic pathway to a broad range of chiral ferrocenes in 40–98 % yield and 93–99 % ee.
Oxidative purification of halogenated ferrocenes
Inkpen, Michael S.,Du, Shuoren,Driver, Mark,Albrecht, Tim,Long, Nicholas J.
, p. 2813 - 2816 (2013)
We report the large scale syntheses and 'oxidative purification' of fcI2, fcBr2 and FcBr (fc = ferrocene-1,1′-diyl, Fc = ferrocenyl). These valuable starting materials are typically laborious to separate via conventional techniques, but can be readily isolated by taking advantage of their increased E1/2 relative to FcH/FcX contaminants. Our work extends this methodology towards a generic tool for the separation of redox active mixtures.
Urea-bridged diferrocene: Structural, electrochemical, and spectroelectrochemical studies
Gong, Zhong-Liang,Zhong, Yu-Wu
, p. 1444 - 1450 (2015)
Urea-bridged diferrocene derivatives N,N′-diferrocenylurea (1) and N,N′-dimethyl-N,N′-diferrocenylurea (2) were prepared and characterized. Single-crystal X-ray analysis shows that Compound 1 has a trans-trans linear conformation whereas Compound 2 has a trans-cis conformation. Both compounds display two consecutive redox couples with, respectively, E1/2 of +0.29 and +0.42 V vs. Ag/AgCl for 1 and +0.31 and +0.50 V for 2. Spectroelectrochemical studies show the presence of distinct intervalence charge transfer (IVCT) transitions for the one-electron-oxidized mixed-valent Compound 1 +, with an estimated electronic coupling parameter of 190 cm-1. By contrast, the one-electron-oxidized Compound 2 + shows much weaker IVCT transitions.
Bis-ferrocenyl-pyridinediimine trinuclear mixed-valent complexes with metal-binding dependent electronic coupling: Synthesis, structures, and redox-spectroscopic characterization
Carter, Cole,Kratish, Yosi,Jurca, Titel,Gao, Yanshan,Marks, Tobin J.
, p. 18715 - 18729 (2020)
A family of metal dichloride complexes having a bisferrocenyl- substituted pyridinediimine ligand was systematically synthesized ((Fc2PDI)MCl2, M = Mg, Zn, Fe, and Co) and characterized crystallographically, spectroscopically, electrochemically, and computationally. Electronic coupling between the ligand ferrocene units is switched on upon binding to a MCl2 fragment, as evidenced by both sequential oxidation of the ferrocenes in cyclic voltammetry (ΔEox ≈ 200 mV) and by Inter-Valence Charge Transfer electronic excitations in the near IR. Additionally, UV-vis spectra are used to directly observe orbital mixing between the ferrocenyl units and the imine π system since breaking of the orbital symmetry results in allowed transitions (? = 2800 M-1cm-1 vs ? ≈ 200 M-1cm-1 in free ferrocene) as well as broadening and red-shifting of the ferrocenyl transitions-indicating organic character in formerly pure metal-centered transitions. DFT analysis reveals that interaction between the ferrocenes and the MCl2 fragment is small and suggests that communication is mediated by better energy matching between the ferrocene and organic π? orbitals upon coordination, allowing superexchange coupling through the LUMO. Furthermore, single crystal diffraction data obtained from oxidation of one and both ferrocenes show distortions, introducing the empty dxy/dx2-y2 orbitals into the secondary coordination sphere of the MCl2 fragment. Such structural rearrangements are infrequent in ferrocenyl mixedvalent compounds, and implications for catalysis as well as electronic communication are discussed.
An environmentally benign and cost-effective synthesis of aminoferrocene and aminoruthenocene
Leonidova, Anna,Joshi, Tanmaya,Nipkow, David,Frei, Angelo,Penner, Johanna-Elena,Konatschnig, Sandro,Patra, Malay,Gasser, Gilles
, p. 2037 - 2040 (2013)
An improved synthesis of aminoferrocene has been carried out that adheres with the basic green chemistry guidelines. Amination from aqueous NH3 as the nitrogen source, with the inexpensive CuI/Fe2O3 couple as cocatalyst in ethanolic solution, makes the process environmentally attractive as well as a viable alternative for all practical purposes. This procedure has also been applied to prepare aminoruthenocene, being reported for the first time.
Syntheses and purification of the versatile synthons iodoferrocene and 1,1′-diiodoferrocene
Roemer, Max,Nijhuis, Christian A.
, p. 11815 - 11818 (2014)
This paper describes the improved synthesis and purification of iodoferrocene (FcI) and 1,1′-diiodoferrocene (FcI2). FcI and FcI2 were prepared by mono- and dilithiation of ferrocene followed by conversion into iodoferrocenes by reaction with iodine. Purification was accomplished by a simple sublimation/distillation procedure, affording FcI and FcI2 in high yields (74 and 72%) and high purity (>99.9%). We determined the molecular structures of FcI and FcI2 by X-ray single crystal diffraction. This journal is the Partner Organisations 2014.
