Single-crystal pulsed neutron diffraction structure of the antiferromagnet K2[FeCl5(H2O)] with and without applied pressure

Schultz, A. J.; Carlin, Richard L.

doi:10.1107/s0108768194008438

Cited by 24 publications

(18 citation statements)

References 5 publications

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“…Details of the data collection and analysis procedures have been published previously. 16 A crystal with approximate dimensions of 3 × 2 × 1 mm 3 and a weight of 5.9 mg, was wrapped in aluminum foil and glued to an aluminum pin that was mounted on the cold stage of a closed-cycle helium refrigerator. The crystal was then cooled under vacuum to 20 ± 1 K. For each setting of the diffractometer angles, data were stored in three-dimensional histogram form with coordinates x, y, t corresponding to horizontal and vertical detector positions and the time-of-flight, respectively.…”

Section: X-ray Datamentioning

confidence: 99%

Structural, theoretical and spectroscopic studies of the dichloride hexahydrate cube [Cl2(H2O)6]2−

et al. 2012

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The structure of the dichloride hexahydrate cube, [Cl(2)(H(2)O)(6)](2-), as a salt with the tris(diisopropylamino)cyclopropenium cation, [C(3)(N(i)Pr(2))(3)](+), has been determined by low-temperature X-ray and neutron-diffraction studies. H atoms not involved in O-H···Cl bonding are disordered over two 0.5 occupancy sites around the O(6) ring. Calculations of the dianionic cube in the gas phase show remarkably good agreement with the solid-state structures with the exception of short O-H bond distances around the O(6) ring that suggests the involvement of a dynamic process. The cluster was also characterised by single-crystal infrared spectroscopy, and vibrational wavenumbers were found to be in good agreement with hydrogen bonding distances. Dibromide and difluoride hexahydrates were also studied theoretically, and O···O distances were found to decrease in the order difluoride > dichloride > dibromide > (H(2)O)(6) and as O···O···O angles increased towards an almost planar ring in (H(2)O)(6). NMR spectra of a chloroform solution of the hydrated salt at -25 °C is consistent with cluster formation.

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Section: X-ray Datamentioning

confidence: 99%

Structural, theoretical and spectroscopic studies of the dichloride hexahydrate cube [Cl2(H2O)6]2−

et al. 2012

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“…FeCl 2 data are from [20], FeOCl data are from [21]. Experimental values of Fe-Cl bond length for FeCl 3 and K 2 FeCl 5 (H 2 O) are from [22] and [23], correspondingly. Red star-experimental point for Na 2 FeCl 4 OH x .…”

Section: Discussionmentioning

confidence: 99%

Interaction Between FeOOH and NaCl at Extreme Conditions: Synthesis of Novel Na2FeCl4OHx Compound

et al. 2020

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Iron(III) oxide-hydroxide, FeOOH, is abundant in the banded iron formations (BIFs). Recent studies indicate that BIFs may carry water down to the lower mantle with subducting slabs. The previous experiments investigating the properties of FeOOH at extreme pressures (P) and temperatures (T) were performed in diamond anvil cells (DACs), where it was compressed inside alkali metal halide pressure-transmitting media (2). Alkali metal halides such as NaCl or KCl are expected to be chemically inert; therefore, they are widely used in DAC experiments. Here, we report the chemical interaction between FeOOH and NaCl pressure medium at 107(2) GPa and 2400(200) K. By means of single-crystal X-ray diffraction (SC-XRD) analysis applied to a multigrain sample, we demonstrate the formation of a Na2FeCl4OHx phase and provide its structural solution and refinement. Our results demonstrate that at high P-T conditions, the alkali metal halides could interact with hydrous phases and thus cannot be used as a pressure transmitting and thermal insulating medium in DAC experiments dedicated to studies of hydroxyl or water-bearing materials at high P-T.

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“…Neutron diffraction data were obtained at the Intense Pulsed Neutron Source (IPNS) at Argonne National Laboratory using the time-of-flight Laue single-crystal diffractometer (SCD). [18][19][20] (H) 4 (4-syn), with approximate dimensions of 2 × 2 × 1 mm 3 and weighing 6.8 mg, was coated with fluorocarbon grease, wrapped in aluminum foil, and glued to an aluminum pin that was mounted on the cold stage of a closedcycle helium refrigerator and cooled to -80(1) °C. Details of the data collection and analysis procedures have been published previously.…”

Section: Methodsmentioning

confidence: 99%

Intramolecular C−H Bond Activation and Redox Isomerization across Two-Electron Mixed Valence Diiridium Cores

et al. 2008

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Metal−metal cooperativity enables the reaction of carbon-based substrates at diiridium two-electron mixed valence centers. Arylation of Ir2 0,II(tfepma)3Cl2 (1) (tfepma = bis[(bistrifluoroethoxy)phosphino]methylamine) with RMgBr (R = C6H5 and C6D5) is followed by C−H bond activation to furnish the bridging benzyne complex Ir2 II,II(tfepma)3(μ-C6H4)(C6H5)H (2), as the kinetic product. At ambient temperature, 2 isomerizes to Ir2 I,III(tfepma)3(μ-C6H4)(C6H5)H (3) (k obs = 9.57 ± 0.10 × 10−5 s−1 at 31.8 °C, ΔH ⧧ = 21.7 ± 0.3 kcal/mol, ΔS ⧧ = −7.4 ± 0.9 eu), in which the benzyne moiety is conserved and the IrIII center is ligated by terminal hydride and phenyl groups. The same reaction course is observed for arylation of 1 with C6D5MgBr to produce 2-d 10 and 3-d 10 accompanied by an inverse isotope effect, k h/k d= 0.44 (k obs = 2.17 ± 0.10 × 10−4 s−1 in C6D6 solution at 31.8 °C, ΔH ⧧ = 24.9 ± 0.7 kcal/mol, ΔS ⧧ = −6.4 ± 2.4 eu). 2 reacts swiftly with hydrogen to provide Ir2 II,II(tfepma)3H4 as both the syn and anti isomers (4-syn and 4-anti, respectively). The hydrides of 4-syn were directly located by neutron diffraction analysis. X-ray crystallographic examination of 2, 2-d 10, 3, and 4-syn indicates that cooperative reactivity at the bimetallic diiridium core is facilitated by the ability of the two-electron mixed valence framework to accommodate the oxidation state changes and ligand rearrangements attendant to the reaction of the substrate.

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Single-crystal pulsed neutron diffraction structure of the antiferromagnet K₂[FeCl₅(H₂O)] with and without applied pressure

Cited by 24 publications

References 5 publications

Structural, theoretical and spectroscopic studies of the dichloride hexahydrate cube [Cl2(H2O)6]2−

Structural, theoretical and spectroscopic studies of the dichloride hexahydrate cube [Cl2(H2O)6]2−

Interaction Between FeOOH and NaCl at Extreme Conditions: Synthesis of Novel Na2FeCl4OHx Compound

Intramolecular C−H Bond Activation and Redox Isomerization across Two-Electron Mixed Valence Diiridium Cores

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