Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Reversible coordination of N2 and H2 to a homoleptic S = 1/2 Fe(i) diphosphine complex in solution and the solid state.

ABSTRACT: The synthesis and characterisation of the S = 1/2 Fe(i) complex [Fe(depe)2]+[BArF4]- ([1]+[BArF4]-), and the facile reversible binding of N2 and H2 in both solution and the solid state to form the adducts [1·N2]+ and [1·H2]+, are reported. Coordination of N2 in THF is thermodynamically favourable under ambient conditions (1 atm; ?G 298 = -4.9(1) kcal mol-1), while heterogenous binding is more favourable for H2 than N2 by a factor of ?300. [1·H2]+[BArF4]- represents a rare example of a well-defined, open-shell, non-classical dihydrogen complex, as corroborated by ESR spectroscopy. The rapid exchange between N2 and H2 coordination under ambient conditions is unique for a paramagnetic Fe complex.

SUBMITTER: Doyle LR

PROVIDER: S-EPMC6237127 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Reversible coordination of N2 and H2 to a homoleptic S = 1/2 Fe(i) diphosphine complex in solution and the solid state.

Doyle Laurence R LR Scott Daniel J DJ Hill Peter J PJ Fraser Duncan A X DAX Myers William K WK White Andrew J P AJP Green Jennifer C JC Ashley Andrew E AE

Chemical science 20180718 37

The synthesis and characterisation of the S = 1/2 Fe(i) complex [Fe(depe)2]+[BArF4]- ([1]+[BArF4]-), and the facile reversible binding of N2 and H2 in both solution and the solid state to form the adducts [1·N2]+ and [1·H2]+, are reported. Coordination of N2 in THF is thermodynamically favourable under ambient conditions (1 atm; ΔG ...[more]

PMID: 30542539

Similar Datasets

Synthesis, Solution and Solid State Structure of Titanium-Maltol Complex.

Project description:The reaction of Cp(2)TiCl(2) with two equivalents of maltol (3-hydroxy-2-methyl-4-pyrone) in water, at room temperature and pH of 5.4, leads to a complete replacement of Cp and chloride ligands affording, Ti(maltolato)(2)(OH)(2.) The complex has been characterized by IR, NMR and ESI-MS spectroscopic and cyclic voltammetry methods. In DMSO-d(6) solution, the complex shows two isomers in a ratio of 4:1, in which one OH signal can be identified per isomer. This suggests that in solution the complex is monomeric, most likely a chiral cis-Ti(maltolato)(2)(OH)(2) and trans-Ti(maltolato)(2)(OH)(2). The monomeric nature of the complex (in water/methanol 1:1) was verified by ESI-MS spectroscopy, showing a parent peak at 329 m/z. Electrochemical behavior of Ti(maltolato)(2)(OH)(2) using cyclic voltammetry experiments showed the complex undergoes irreversible reduction in aprotic solvents. In D(2)O solution, at pH of 8.4, the (1)H NMR spectrum of the complex shows a mixture of monomer and tetramer Ti(IV)-maltol complexes in a ratio of 1:1. The crystallization of Ti(maltolato)(2)(OH)(2) at pH of 8.4 leads to the formation of [Ti(4)(maltolato)(8)(?-O(4))]•18H(2)O. A single crystal of [Ti(4)(maltolato)(8)(?-O(4))]•18H(2)O was analyzed by X-ray diffraction methods. The complex crystallizes in a monoclinic space group P2(1)/c with a = 12.617(4) Å, b = 24.058(8) Å, c = 22.686(7) Å, ?= 97.678(4)° and V = 6824(4) Å(3) for Z = 4. Solid state structure determination of the Ti-maltol complex showed to be tetrameric, containing two bridging oxides (in cis position) and two bidentate maltol ligands per titanium in a pseudo-octahedral coordination geometry.

| S-EPMC1948875 | biostudies-literature

Dirhenium Coordination Complex Endowed with an Intrinsically Chiral Helical-Shaped Diphosphine Oxide.

Project description:A one-pot, multicomponent strategy was used to synthesize the first example of the dirhenium carbonyl coordination complex 2, in which the two metal atoms are connected through a chiral helical-shaped diphosphine oxide. Thanks to the flexibility of the helix of helicene 1, complex 2 was isolated in quite a good yield as a stable compound. It was characterized by analytical and spectroscopic techniques as well as by single-crystal X-ray analysis, which confirmed the chemical structure and the peculiar architecture of 2. In addition, computational studies were in agreement with the transitions observed in the experimental UV-vis spectrum, revealing the presence of two bands with maxima at about 520 (metal-to-ligand charge transfer) and 400 nm (IL).

| S-EPMC6645470 | biostudies-literature

Phenolacetyl Viologen as Multifunctional Chromic Material for Fast and Reversible Sensor of Solvents, Base, Temperature, Metal Ions, NH3 Vapor, and Grind in Solution and Solid State.

Project description:Electron-withdrawing/coordinating o-phenolacetyl-substituted viologen can act as a visual sensor for solvents, bases, and temperature in organic solvents. Due to chelating phenolacetyl groups, this viologen can coordinate to Fe(III), Cu(II), and ZnCl2 in aqueous and DMF solutions. Interestingly, this viologen can respond to temperature, grind, and NH3 vapor in its solid state. Stimuli response is visible, fast, and fully reversible in air at room temperature. The color change is attributed to the enolic and/or free radical structure. This is the most versatile chromic material that responds to chemical and physical stimuli in both solution and solid state.

| S-EPMC6641105 | biostudies-literature

Chemical Bonding in Homoleptic Carbonyl Cations [M{Fe(CO)5 }2 ]+ (M=Cu, Ag, Au).

Project description:Syntheses of the copper and gold complexes [Cu{Fe(CO)5 }2 ][SbF6 ] and [Au{Fe(CO)5 }2 ][HOB{3,5-(CF3 )2 C6 H3 }3 ] containing the homoleptic carbonyl cations [M{Fe(CO)5 }2 ]+ (M=Cu, Au) are reported. Structural data of the rare, trimetallic Cu2 Fe, Ag2 Fe and Au2 Fe complexes [Cu{Fe(CO)5 }2 ][SbF6 ], [Ag{Fe(CO)5 }2 ][SbF6 ] and [Au{Fe(CO)5 }2 ][HOB{3,5-(CF3 )2 C6 H3 }3 ] are also given. The silver and gold cations [M{Fe(CO)5 }2 ]+ (M=Ag, Au) possess a nearly linear Fe-M-Fe' moiety but the Fe-Cu-Fe' in [Cu{Fe(CO)5 }2 ][SbF6 ] exhibits a significant bending angle of 147° due to the strong interaction with the [SbF6 ]- anion. The Fe(CO)5 ligands adopt a distorted square-pyramidal geometry in the cations [M{Fe(CO)5 }2 ]+ , with the basal CO groups inclined towards M. The geometry optimization with DFT methods of the cations [M{Fe(CO)5 }2 ]+ (M=Cu, Ag, Au) gives equilibrium structures with linear Fe-M-Fe' fragments and D2 symmetry for the copper and silver cations and D4d symmetry for the gold cation. There is nearly free rotation of the Fe(CO)5 ligands around the Fe-M-Fe' axis. The calculated bond dissociation energies for the loss of both Fe(CO)5 ligands from the cations [M{Fe(CO)5 }2 ]+ show the order M=Au (De =137.2 kcal mol-1 )>Cu (De =109.0 kcal mol-1 )>Ag (De =92.4 kcal mol-1 ). The QTAIM analysis shows bond paths and bond critical points for the M-Fe linkage but not between M and the CO ligands. The EDA-NOCV calculations suggest that the [Fe(CO)5 ]→M+ ←[Fe(CO)5 ] donation is significantly stronger than the [Fe(CO)5 ]←M+ →[Fe(CO)5 ] backdonation. Inspection of the pairwise orbital interactions identifies four contributions for the charge donation of the Fe(CO)5 ligands into the vacant (n)s and (n)p AOs of M+ and five components for the backdonation from the occupied (n-1)d AOs of M+ into vacant ligand orbitals.

| S-EPMC8252735 | biostudies-literature

Solution-Deposited Solid-State Electrochromic Windows.

Project description:Commercially available electrochromic (EC) windows are based on solid-state devices in which WO3 and NiOx films commonly serve as the EC and counter electrode layers, respectively. These metal oxide layers are typically physically deposited under vacuum, a time- and capital-intensive process when using rigid substrates. Herein we report a facile solution deposition method for producing amorphous WO3 and NiOx layers that prove to be effective materials for a solid-state EC device. The full device containing these solution-processed layers demonstrates performance metrics that meet or exceed the benchmark set by devices containing physically deposited layers of the same compositions. The superior EC performance measured for our devices is attributed to the amorphous nature of the NiOx produced by the solution-based photodeposition method, which yields a more effective ion storage counter electrode relative to the crystalline NiOx layers that are more widely used. This versatile method yields a distinctive approach for constructing EC windows.

| S-EPMC6277218 | biostudies-literature

Reversible Encapsulation of Xenon and CH2 Cl2 in a Solid-State Molecular Organometallic Framework (Guest@SMOM).

Project description:Reversible encapsulation of CH2 Cl2 or Xe in a non-porous solid-state molecular organometallic framework of [Rh(Cy2 PCH2 PCy2 )(NBD)][BArF 4 ] occurs in single-crystal to single-crystal transformations. These processes are probed by solid-state NMR spectroscopy, including 129 Xe SSNMR. Non-covalent interactions with the -CF3 groups, and hydrophobic channels formed, of [BArF 4 ]- anions are shown to be important, and thus have similarity to the transport of substrates and products to and from the active site in metalloenzymes.

| S-EPMC6899477 | biostudies-literature

The Synthesis of LiMnxFe1-xPO?/C Cathode Material through Solvothermal Jointed with Solid-State Reaction.

Project description:LiMnxFe1-xPO?/C material has been synthesized through a facile solid-state reaction under the condition of carbon coating, using solvothermal-prepared LiMnPO? and LiFePO? as precursors and sucrose as a carbon resource. XRD and element distribution analysis reveal completed solid-state reaction of precursors. LiMnxFe1-xPO?/C composites inherit the morphology of precursors after heat treatment without obvious agglomeration and size increase. LiMnxFe1-xPO? solid solution forms at low temperature around 350 °C, and Mn2+/Fe2+ diffuse completely within 1 h at 650 °C. The LiMnxFe1-xPO?/C (x < 0.8) composite exhibits a high-discharge capacity of over 120 mAh·g-1 (500 Wh·kg-1) at low C-rates. This paves a way to synthesize the crystal-optimized LiMnxFe1-xPO?/C materials for high performance Li-ion batteries.

| S-EPMC5457063 | biostudies-literature

Facile synthesis of carbon nanotube-supported NiO//Fe2O3 for all-solid-state supercapacitors.

Project description:We have successfully prepared iron oxide and nickel oxide on carbon nanotubes on carbon cloth for the use in supercapacitors via a simple aqueous reduction method. The obtained carbon cloth-carbon nanotube@metal oxide (CC-CNT@MO) three-dimensional structures combine the high specific capacitance and rich redox sites of metal oxides with the large specific area and high electrical conductivity of carbon nanotubes. The prepared CC-CNT@Fe2O3 anode reaches a high capacity of 226 mAh·g-1 at 2 A·g-1 with a capacitance retention of 40% at 40 A·g-1. The obtained CC-CNT@NiO cathode exhibits a high capacity of 527 mAh·g-1 at 2 A·g-1 and an excellent rate capability with a capacitance retention of 78% even at 40 A·g-1. The all-solid-state asymmetric supercapacitor fabricated with these two electrodes delivers a high energy density of 63.3 Wh·kg-1 at 1.6 kW·kg-1 and retains 83% of its initial capacitance after 5000 cycles. These results demonstrate that our simple aqueous reduction method to combine CNT and metal oxides reveals an exciting future in constructing high-performance supercapacitors.

| S-EPMC6774069 | biostudies-literature

PAH/PAH(CF3 )n Donor/Acceptor Charge-Transfer Complexes in Solution and in Solid-State Co-Crystals.

Project description:A solution, solid-state, and computational study is reported of polycyclic aromatic hydrocarbon PAH/PAH(CF3 )n donor/acceptor (D/A) charge-transfer complexes that involve six PAH(CF3 )n acceptors with known gas-phase electron affinities that range from 2.11(2) to 2.805(15) eV and four PAH donors, including seven CT co-crystal X-ray structures that exhibit hexagonal arrays of mixed π-stacks with 1/1, 1/2, or 2/1 D/A stoichiometries (PAH=anthracene, azulene, coronene, perylene, pyrene, triphenylene; n=5, 6). These are the first D/A CT complexes with PAH(CF3 )n acceptors to be studied in detail. The nine D/A combinations were chosen to allow several structural and electronic comparisons to be made, providing new insights about controlling D/A interactions and the structures of CT co-crystals. The comparisons include, among others, CT complexes of the same PAH(CF3 )n acceptor with four PAH donors and CT complexes of the same donor with four PAH(CF3 )n acceptors. All nine CT complexes exhibit charge-transfer bands in solution with λmax between 467 and 600 nm. A plot of E(λmax ) versus [IE(donor)-EA(acceptor)] for the nine CT complexes studied is linear with a slope of 0.72±0.03 eV eV-1 . This plot is the first of its kind for CT complexes with structurally related donors and acceptors for which precise experimental gas-phase IEs and EAs are known. It demonstrates that conclusions based on the common assumption that the slope of a CT E(λmax ) versus [IE-EA] plot is unity may be incorrect in at least some cases and should be reconsidered.

| S-EPMC6916568 | biostudies-literature

Photophysical Properties of Cyclometalated Platinum(II) Diphosphine Compounds in the Solid State and in PMMA Films.

Project description:Platinum(II) compounds were synthesized with both chelate cyclometalated ligands and chelate diphosphine ligands. The cyclometalated ligands include phenylpyridine and a benzothiophene-containing ligand. The three new benzothiophene compounds were characterized by nuclear magnetic resonance (NMR) spectroscopy, high-resolution mass spectrometry (HR-MS), and photophysical measurements. In the case of one compound, L1-DPPM, the structure was determined by single crystal X-ray diffraction. The structural coherence of the noncrystalline emissive solid state was measured by X-ray total scattering real space pair distribution function analysis. Quantum yield values of all of the platinum compounds measured in the solid state and in PMMA films were much greater than in solution.

| S-EPMC8552474 | biostudies-literature