Showing papers on "Ferrocene published in 2016"
TL;DR: In this article, it is shown that nanostructured pseudocapacitive electrodes functionalized with ferrocene-based redox polymers are an attractive platform for the selective sorptive separation of dilute organic anions from strong aqueous and organic electrolyte solutions, and subsequent release of the sorbed ions to a stripping phase through electrochemical control of specific binding processes.
Abstract: Redox species have been explored extensively for catalysis, energy storage, and molecular recognition. It is shown that nanostructured pseudocapacitive electrodes functionalized with ferrocene-based redox polymers are an attractive platform for the selective sorptive separation of dilute organic anions from strong aqueous and organic electrolyte solutions, and subsequent release of the sorbed ions to a stripping phase through electrochemical control of the specific binding processes. A remarkable degree of selectivity is shown for carboxylates (–COO–), sulfonates (–SO3−), and phosphonates (–PO3−2) over inorganic anions such as PF6− and ClO4− (separation factor >140 in aqueous and >3000 in organic systems), and between carboxylates with various substituents, based on differences in electronic structure and density of the adsorbates, beyond size, and charge. Our organometallic redox electrodes are a promising platform for targeting aqueous and organic systems requiring high separation factors and fast throughput, such as in the recovery of value-added products from organic synthesis and isolation of dilute yet highly toxic organic contaminants. The combination of spectroscopic experiments and quantum chemistry sheds light on a selective binding mechanism based on redox-enhanced hydrogen bonding between the cyclopentadienyl ligand and the carboxylate functional group, with broader implications for molecular design, supramolecular recognition, and metallocene catalysis.
98 citations
TL;DR: The synthesis and isolation of ferrocene salts with iron in the +4 state are reported, which are characterized crystallographically and spectroscopically and surprisingly stable Fe(IV) salts of the [Cp*2Fe]2+ dication.
Abstract: Ferrocene and its decamethyl derivative [Cp*2Fe] are the most common standards for nonaqueous electrochemical investigations because of their well-defined and only mildly solvent-dependent reversible Fe(II)/Fe(III) redox couple. Higher oxidation states have only rarely been studied. We report the isolation and crystallographic and spectroscopic characterization of surprisingly stable Fe(IV) salts of the [Cp*2Fe]2+ dication, produced by oxidation of [Cp*2Fe] with AsF5, SbF5, or ReF6 in neat sulfur dioxide as well as [XeF](Sb2F11) in neat hydrogen fluoride. The Sb2F11– salt exhibits a metallocene with the expected mutually parallel arrangements of the Cp* rings, whereas the As2F11–, AsF6–, SbF6–, and ReF6– salts manifest tilt angles ranging from 4° to 17°. Both 57Fe Mossbauer spectroscopy and superconducting quantum interference device magnetization studies reveal identical d-orbital splitting with an S = 1, 3E ground state based on the 3d electronic configuration e2g3a1g1 of all [Cp*2Fe]2+ salts.
80 citations
TL;DR: This review will focus on the exploitation of ferrocene (and related sandwich complexes) for the development of non-interlocked synthetic molecular machines.
72 citations
TL;DR: The synthesis and properties of the first family of molecules belonging to this compound category-differently sized rings comprising only 1,1'-disubstituted ferrocene units (cyclo[n], n = 5-7, 9) are described.
Abstract: Cyclic molecules often exhibit unusual properties; consider for example the resonance stabilization energy of benzene or the strong cation binding of crown ethers. Now, a family of rings comprising varying numbers of directly linked ferrocenes has been prepared. These compounds are highly symmetric in solution and undergo rapid ‘oxidation-state isomerism’ when charged.
69 citations
TL;DR: The observed enhancement correlates with lower electron-density on the ferrocene; the synergistic improvement observed for mixtures of substituted ferrocenes and iodine is attributed to the formation of charge-transfer complexes.
53 citations
TL;DR: Mediated redox catalysis of H2O2 and bio-functionalization with glucose oxidase for glucose detection were achieved by the bioelectrode providing a proof for potential biosensing applications.
49 citations
TL;DR: The electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer, and possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine are demonstrated.
Abstract: Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free e...
49 citations
TL;DR: In this paper, the synthesis of ferrocene-based pyridinones via Rh(III)-catalyzed annulation of Ferrocenecarboxamides with internal alkynes has been developed using a directing group as the internal oxidant.
48 citations
TL;DR: In this article, six novel ferrocene-based polyethyleneimines (PEI-Fcs) were synthesized by the condensation reaction of branched polyethylenecarbonyl chloride.
Abstract: Ferrocene-based polymers and their derivatives have the ability to catalyze the burning process of composite solid propellants efficiently. However, the simple and volatile ferrocene migrates to the surface of the solid propellant on prolonged storage, which alters the designed burning parameters and more seriously causes unexpected explosions. To retard migration problems, six novel ferrocene-based polyethyleneimines (PEI-Fcs) were synthesized by the condensation reaction of branched polyethyleneimine (PEI) with ferrocenecarbonyl chloride. The structures of the synthesized PEI-Fcs were characterized using 1H NMR, FT-IR and UV-Vis spectroscopy. The redox properties of the polymers are very important for burning rate catalysts (BRCs). Cyclic voltammetry (CV) revealed that all the PEI-Fcs showed redox properties due to the presence of ferrocene moieties. Migration studies confirmed that the migration of these PEI-Fcs was much slower than that of 2,2-bis(ethylferrocenyl)propane (catocene) and ferrocene. The catalytic effect of PEI-Fcs on the thermal decomposition of ammonium perchlorate (AP) was investigated using thermogravimetry (TG) and differential thermogravimetry (DTG). It was found that in the presence of PEI-Fcs (1–6), the peak decomposition temperature of AP was shifted towards the left (decreased) significantly. The results from the TG and DTG analysis indicated that the novel PEI-Fcs had good catalytic effects of lowering the thermal decomposition temperature of AP and were almost stable up to 220 °C. We expect that these novel PEI-Fcs would have great value as high BRCs for composite solid propellants.
47 citations
TL;DR: A homochiral, square-shaped, D2 symmetrical nanosized metal-linked macrocycle is able to form stable complexes with ferrocene in polar solvents, with detection achieved by means of multiple outputs.
47 citations
TL;DR: With combined spectroscopic studies and theoretical calculations, it was determined that effective polysulfide binding originates from favorable cation-π interactions between Li+ of lithiumpolysulfides and the negatively charged cyclopentadienyl ligands of ferrocene.
Abstract: Confining lithium polysulfide intermediates is one of the most effective ways to alleviate the capacity fade of sulfur-cathode materials in lithium–sulfur (Li–S) batteries. To develop long-cycle Li–S batteries, there is an urgent need for material structures with effective polysulfide binding capability and well-defined surface sites; thereby improving cycling stability and allowing study of molecular-level interactions. This challenge was addressed by introducing an organometallic molecular compound, ferrocene, as a new polysulfide-confining agent. With ferrocene molecules covalently anchored on graphene oxide, sulfur electrode materials with capacity decay as low as 0.014 % per cycle were realized, among the best of cycling stabilities reported to date. With combined spectroscopic studies and theoretical calculations, it was determined that effective polysulfide binding originates from favorable cation–π interactions between Li+ of lithium polysulfides and the negatively charged cyclopentadienyl ligands of ferrocene.
TL;DR: The smallest and most strained member of a family of π‐conjugated cyclic porphyrin oligomers was synthesized by using pentapyridyl templates based on ferrocene and corannulene to directing the synthesis of the butadiyne‐linked cyclic pentamer.
Abstract: The smallest and most strained member of a family of π-conjugated cyclic porphyrin oligomers was synthesized by using pentapyridyl templates based on ferrocene and corannulene. Both templates are effective for directing the synthesis of the butadiyne-linked cyclic pentamer, despite the fact that the radii of their N5 donor sets are too small by 0.5 A and 0.9 A, respectively (from DFT calculations). The five-porphyrin nanoring exhibits a structured absorption spectrum and its fluorescence extends to 1200 nm, reflecting strong π conjugation and Herzberg–Teller vibronic coupling.
TL;DR: In this paper, a new anthracenyl-appended ferrocene bearing the aniline N and the thiourea S donors for multiple signaling sensing of metal ions, has been synthesized and characterized.
Abstract: A new anthracenyl-appended ferrocene bearing the aniline N and the thiourea S donors ( 1 ) for multiple signaling sensing of metal ions, has been synthesized and characterized. Upon addition of various metal ions in CH 3 CN solution, 1 shows a distinctive response to Cu 2+ and Hg 2+ over other metal ions, with a large enhancement of the emission of 1 , and an anodic shift of electrochemical potential. In contrast, in CH 3 CN–Tris (1:1, v/v) buffer solution, 1 only shows a fluorescence turn-on response to Hg 2+ over other metal ions, which can distinguish Hg 2+ from Cu 2+ and other metal ions. Furthermore, the supposed binding mode of 1 with Hg 2+ and/or Cu 2+ was also discussed according to the 1 H NMR titration and the theoretical calculation results by density functional theory (DFT) method.
TL;DR: The first tetrahedral cobalt salen (salen = N,N′-ethylenesalicylimine) complex was synthesized by using a 1,1′-ferrocene derivative, salfen as discussed by the authors.
TL;DR: Though the structure details as well as spectroscopic characterizations of 5 are yet to be investigated, the compound 7 is fully characterized by variety of spectroscopy including single-crystal X-ray diffraction.
Abstract: A series of compounds, namely, [Cu8(μ4-H){S2CNMeCH2Fc}6](PF6) (1), [Cu7(μ4-H) {S2CNiPrCH2Fc}6] (2), [Cu3{S2CN(Bz) (CH2Fc)}2(dppf)2](PF6) (3), and [Ag2{S2CNMe(CH2Fc)}2(PPh3)2] (4) (dppf = 1,1′-bis(diphenylphosphino)ferrocene), supported by multiferrocene assemblies, were synthesized. All the compounds were characterized by 1H NMR, Fourier transform infrared, elemental analysis, and electrospray ionization mass spectrometry techniques. Single-crystal X-ray structural analysis revealed that 1 is a monocationic octanuclear CuI cluster and that 2 is a neutral heptanuclear CuI cluster with tetracapped tetrahedral (1) and tricapped tetrahedral (2) geometries entrapped with an interstitial hydride, anchored by six ferrocene units at the periphery of the core. Compounds 3 and 4 comprise trimetallic CuI and dimetallic AgI cores enfolded by four and two ferrocene moieties. Interestingly both chelating and bridging modes of binding are observed for dppf ligand in 3. Further the formation and isolation of polyhydrido ...
TL;DR: Systematic studies employing X-ray crystallography, spectroscopy, cyclic voltammetry, and density functional theory calculations revealed that the ferrocene backbone could stabilize the electron-deficient metal through a donor-acceptor-type interaction.
Abstract: Our group has focused on the organometallic chemistry of rare-earth metals and actinides for a decade. By installing ferrocenediamide ligands at electropositive metal centers, we have been able to disclose unprecedented reactivity toward aromatic N-heterocycles, arenes, and other small molecules such as P4. Systematic studies employing X-ray crystallography, spectroscopy, cyclic voltammetry, and density functional theory calculations revealed that the ferrocene backbone could stabilize the electron-deficient metal through a donor-acceptor-type interaction. Most noteworthy is that this interaction can be readily turned on or off by the addition or removal of a Lewis base. In addition to its flexible coordination, the redox-active nature of the ferrocene backbone enabled us to explore redox-switchable transformations. The introduction of ferrocene-based ligands into organolanthanide chemistry not only helped us to study intriguing fundamental problems but also led to fruitful chemistry including small-molecule activation and controlled copolymerization reactions.
TL;DR: It is found that unlike single ferrocene a CoFc molecule possesses a magnetic moment as revealed by the Kondo effect, which corresponds to the first controlled procedure toward the development of tailored metallocene-based nanowires with a desired chemical composition.
Abstract: The manipulation of the molecular spin state by atom doping is an attractive strategy to confer desirable magnetic properties to molecules. Here, we present the formation of novel magnetic metallocenes by following this approach. In particular, two different on-surface procedures to build isolated and layer-integrated Co-ferrocene (CoFc) molecules on a metallic substrate via atomic manipulation and atom deposition are shown. The structure as well as the electronic properties of the so-formed molecule are investigated combining scanning tunneling microscopy and spectroscopy with density functional theory calculations. It is found that unlike single ferrocene a CoFc molecule possesses a magnetic moment as revealed by the Kondo effect. These results correspond to the first controlled procedure toward the development of tailored metallocene-based nanowires with a desired chemical composition, which are predicted to be promising materials for molecular spintronics.
TL;DR: In this article, three d10 transition-metal dithiocarbamates containing ferrocene were synthesized and characterized by elemental analyses, IR, 1H, and 13C NMR spectroscopy, and X-ray crystallography.
Abstract: Three new d10 transition-metal dithiocarbamates containing ferrocene, namely [M(FcCH2EtOHdtc)2] (M = Zn, Cd and Hg; dtc = dithiocarbamate) have been synthesized and characterized by elemental analyses, IR, 1H, and 13C NMR spectroscopy, and X-ray crystallography. The coordination geometries around the zinc and mercury ions in the complexes are distorted tetrahedral and distorted linear, respectively. The distorted linear geometry around the mercury complex can be attributed to the presence of the bulky methylferrocenyl groups. These complexes have been used in dye-sensitized solar cells (DSSCs) as co-sensitizers and co-adsorbents. The assembly fabricated by using the zinc complex and N719 (Zn/N719) showed the best performance with an overall photon-to-current conversion efficiency (PCE) of 7.10±0.02%, which is an improvement of 23% in the cell performance compared with the DSSC fabricated by using N719 (PCE 5.76±0.04%) alone under identical conditions. Three new d10 transition-metal dithiocarbamates containing ferrocene have been synthesized and their application as co-sensitizers to the state-of-the-art dye N719 in dye-sensitized solar cells explored.
TL;DR: In this article, a review summarizes recent progress in ferrocene- and azobenzene-based photoelectric responsive materials, including their synthesis, properties and applications, which can be used for wide range of applications like high density information storage, ion recognition, DNA detection, etc.
Abstract: Ferrocene and its derivatives are commonly used electrochemically responsive materials Ferrocene derivatives have attracted much attention due to their high chemical stability, characteristic electrochemical response and high liquid crystallinity Azobenzene and its derivatives are important light responsive materials and possess outstanding photochemical properties due to the presence of an azo bond which can isomerize reversibly between trans- and cis-forms under different illumination conditions These kinds of compounds have been designed for information storage devices, molecular switches, molecular devices and so on By combining a ferrocene group with an azobenzene group, novel functional materials with outstanding properties of both ferrocene and azobenzene can be obtained These novel functional materials can be used for wide range of applications like high density information storage, ion recognition, DNA detection, etc This review summarizes recent progress in ferrocene- and azobenzene-based photoelectric responsive materials, including their synthesis, properties and applications
TL;DR: In this article, a review of the synthesis and catalytic properties of ferrocene-based polymers and derivatives as burning rate catalysts is presented, where two main aspects of anti-migratory exploration are summarized.
Abstract: Burning rate catalysts are of great importance in solid composite propellants for their unique property of accelerating combustion speed. Among various kinds of burning rate catalysts, ferrocene and its derivatives exhibit excellent catalytic effects and have become the most widely used burning rate catalysts. However, these simple ferrocenyl compounds trend to migrate in solid composite propellants during storage, which causes great damage to the propellants, equipment and environment and can even affect personal safety. The exploration of novel anti-migratory ferrocene-based compounds has become an advanced research hotspot in the field of burning rate catalysis. This review focuses on recent progress on the synthesis and catalytic properties of ferrocene-based polymers and ferrocene derivatives as burning rate catalysts. Two main aspects of anti-migratory exploration, i.e. synthesis of ferrocene-based polymers and modification of the side groups of ferrocene, are summarized. Ferrocene-based polymers can be obtained via condensation polymerization, addition polymerization, ring-opening polymerization, polymer reactions, etc. Ferrocenyl compounds with active groups and ferrocene-based metal coordination compounds were developed instead of the methods of lengthening the carbon chain of side groups and improving molecular polarity. Also, possible mechanisms of burning rate catalytic activity and migration are discussed and analyzed. Finally, the key points of the development of ferrocene-based burning rate catalysts and solid composite propellants are proposed. Copyright © 2016 John Wiley & Sons, Ltd.
TL;DR: In this article, Ferrocene and ferrocenophane-based β-diketones and their Cu(II) and Zn-II complexes have been synthesized and characterized.
Abstract: Ferrocene and [3]ferrocenophane-based β-diketones and their Cu(II) and Zn(II) complexes have been synthesized and characterized. Single-crystal X-ray diffraction analysis confirmed the molecular structures of the Cu(II) complexes. UV-vis spectroscopy and electrochemical measurements were obtained. All the new compounds showed quasireversible and diffusion-controlled redox processes. The complexes displayed high thermal stability according to the thermogravimetry (TG) measurements. The β-diketone ligands and complexes exhibited high catalytic effects on the thermal degradation of ammonium perchlorate (AP) which was evaluated by TG and differential scanning calorimetry techniques, whereas the addition of Cu(II) complexes lowered the thermal decomposition temperature of AP more dramatically and released more heat compared with the addition of β-diketone ligands or Zn(II) complexes. We expect that this kind of transition metal complexes containing ferrocenyl would has great value in preparing a high burning rate catalyst for composite solid propellants.
TL;DR: An exhaustive exploration of the potential energy surfaces of ferrocene, ruthenocene and osmocene dimers reveals that inclusion of entropic factors modifies the relative stability of the complexes and indicates that dispersion is the major contributing factor in stabilizing a metallocene dimer.
Abstract: An exhaustive exploration of the potential energy surfaces of ferrocene, ruthenocene and osmocene dimers has been performed. Our computations involving dispersion show that only four different isomers are present in each metallocene dimer. The collective action of small interaction energies of dispersive nature leads to a dissociation energy of 7.5 kcal mol−1 for the ferrocene dimer. Dispersion has strong effects on the geometrical parameters, reducing the M⋯M distances by almost 1 A. Our results also reveal that inclusion of entropic factors modifies the relative stability of the complexes. The nature of bonding is examined using the energy decomposition analysis and the non-covalent interaction index. Both analyses indicate that dispersion is the major contributing factor in stabilizing a metallocene dimer.
TL;DR: In this article, the effects of substituting an electron-withdrawing acetyl group with a polar acyclic group were examined on the performance of a Li/AcFc coin-type non-flowing cell.
TL;DR: The thermally-triggered n-type doping of single-walled carbon nanotubes is demonstrated using 1,1'-bis(diphenylphosphino)ferrocene, a novel n- type dopant, which enables the large-scale fabrication of thermoelectric materials showing an excellent power factor.
Abstract: The thermally-triggered n-type doping of single-walled carbon nanotubes is demonstrated using 1,1'-bis(diphenylphosphino)ferrocene, a novel n-type dopant. Through a simple thermal vacuum process, the phosphine compounds are moderately encapsulated inside single-walled carbon nanotubes. The encapsulation into SWNTs is carefully characterized using Raman/X-ray spectroscopy and transmission electron microscopy. This easy-to-handle doping with air-stable precursors for n-type SWNTs enables the large-scale fabrication of thermoelectric materials showing an excellent power factor exceeding approximately 240 μW mK(-2) .
TL;DR: The complexation between Al(C6F5)3 and ferrocene has been studied, which affords a stable adduct formed through the η(1)-coordination of Al to one of the CCp atoms, similar to the alane-toluene or benzene complex.
Abstract: Alkyl/aryl ligand exchange between AlEt3 and B(C6F5)3 in hexanes enables the formation and isolation of the unsolvated Al(C6F5)3 as a crystalline solid, the structure of which has been determined by single-crystal X-ray diffraction analysis. Instead of forming the anticipated AlF contacts with the seemingly more accessible meta- and para-F's of -C6F5 groups, two Al(C6F5)3 molecules form a dimeric structure with double AlF interactions between the Al center of one molecule and the ortho-F atom of the -C6F5 group on the other molecule. This mode of interactions is apparently linked to the thermal and shock sensitivity of the unsolvated Al(C6F5)3 in the solid state. To compare with the B(C6F5)3/ferrocene frustrated Lewis pair system, the complexation between Al(C6F5)3 and ferrocene has also been studied, which affords a stable adduct formed through the η(1)-coordination of Al to one of the CCp atoms, similar to the alane-toluene or benzene complex.
TL;DR: All the synthetic routes to water-soluble metallocene containing polymers are collected and discussed here and the focus is on neutral ferrocene- and ruthenocene-containing and charged cobaltocenium-containing macromolecules (i.e., symmetrical sandwich complexes).
Abstract: Metallocenes are organometallic compounds with reversible redox profiles and tunable oxidation and reduction potentials, depending on the metal and substituents at the cyclopentadienyl rings. Metallocenes have been introduced in macromolecules to combine the redox-activity with polymer properties. There are many examples of such hydrophobic polymer materials, but much fewer water-soluble examples are found scattered across the polymer literature. However, in terms of drug delivery and other biological applications, water solubility is essential. For this very reason, all the synthetic routes to water-soluble metallocene containing polymers are collected and discussed here. The focus is on neutral ferrocene- and ruthenocene-containing and charged cobaltocenium-containing macromolecules (i.e., symmetrical sandwich complexes). The synthetic protocols, self-assembly behavior, and other benefits of the obtained materials are discussed.
TL;DR: In this paper, 3-(Ferrocenylcarbonyl)propionic acid diglycidyl ester (FCPADE) was synthesized by Friedel-Craft acylation of ferrocene with succinic anhydride followed by reaction with epichlorohydrin.
Abstract: 3-(Ferrocenylcarbonyl)propionic acid diglycidyl ester (FCPADE) was synthesized by Friedel–Craft acylation of ferrocene with succinic anhydride followed by reaction with epichlorohydrin. The synthesis of FCPADE was confirmed by 1H-NMR, 13C-NMR, MS and FT-IR. The electrochemical behavior and catalytic performance on decomposition of ammonium perchlorate (AP) were investigated. The results showed that FCPADE has a good catalytic effect on lowering the thermal decomposition temperature of AP. Anti-migration studies showed that FCPADE has a better anti-migration performance than ferrocene and catocene.
TL;DR: These studies demonstrate that NAMI-A-type compounds can be functionalized with redox-active ligands to produce both cytotoxic and anti-metastatic activity.
Abstract: A series of novel ferrocene (Fc) functionalized Ru(III) complexes was synthesized and characterized. These compounds are derivatives of the anti-metastatic Ru(III) complex imidazolium [trans-RuCl4(1H-imidazole) (DMSO-S)] (NAMI-A) and are derived from its pyridine analogue (NAMI-Pyr), with direct coupling of Fc to pyridine at the 4 or 3 positions, or at the 4 position via a two-carbon linker, which is either unsaturated (vinyl) or saturated (ethyl). Electron paramagnetic resonance (EPR) and UV–vis spectroscopic studies of the ligand exchange processes of the compounds in phosphate buffered saline (PBS) report similar solution behavior to NAMI-Pyr. However, the complex with Fc substitution at the 3 position of the coordinated pyridine shows greater solution stability, through resistance to the formation of oligomeric species. Further EPR studies of the complexes with human serum albumin (hsA) indicate that the Fc groups enhance noncoordinate interactions with the protein and help to inhibit the formation of...
TL;DR: In this article, a new approach was proposed for ferrocene phosphorylation using α-hydroxylalkylphosphonate as a masked phosphorylating agent, by electrochemical reduction of a (Me)2C(OH)P(O)(OC2H5)2 mixture at −50 °C.
Abstract: A new approach is proposed for ferrocene phosphorylation using α-hydroxylalkylphosphonate as a “masked” phosphorylating agent, by electrochemical reduction of a ferrocene and (Me)2C(OH)P(O)(OC2H5)2 mixture at −50 °C. The method makes it possible to obtain the product of diethyl ferrocenyl phosphonate with a high yield (87–89%) and 100% conversion of the initial phosphonate in one stage. It is evidenced with experiments that ferrocene reduction is carried out with preservation of the iron charge in the ferrocene fragment and with the formation of a cyclopentadienyl ligand radical anion at −3.3 V ref. Ag/AgCl (at −50 °C).
TL;DR: In this paper, a flexible and hydrolytically stable metal-organic framework [Mn(H2O)2(Fc(PHOO)2)·2H 2O]n has been synthesized using ferrocene-based ligand bearing phosphinic groups.
Abstract: A flexible and hydrolytically stable metal–organic framework [Mn(H2O)2(Fc(PHOO)2)·2H2O]n has been synthesized using ferrocene-based ligand bearing phosphinic groups (Fc(PHOOH)2 = 1,1′-ferrocenediyl-bis(H-phosphinic acid)). In this compound manganese atoms are bound by phosphinate fragments to give infinite chains, and the latter are interconnected by ferrocene groups to form two-dimensional coordination polymer. The elimination of both coordinated and lattice water molecules during heating up to 150 °C produced the compound, which is nonporous for nitrogen, but can selectively adsorb water over methanol and other solvents at 298 K. The reversible structural transformation during adsorption/desorption of water is also reflected in a change of magnetic properties of the metal–organic framework.