Thermal Detection, Synthesis, and Structural Characterization of Compounds in the Co–W–Cl System

Mos, Agnieszka; Ströbele, Markus; Meyer, H.‐Jürgen

doi:10.1007/s10876-014-0742-0

Cited by 10 publications

(16 citation statements)

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“…Single crystals have been previously obtained by sublimation, and the crystal structure has been characterized as (Fe) intercalated (α-)WCl 6 structure. 9 With increasing Fe content, we expected Fe x WCl 6 to decompose into WCl 5 (W 2 Cl 10 ) and FeCl 2 . Corresponding behavior was obtained for decomposition of LiWCl 6 with formation of WCl 5 and LiCl.…”

Section: ■ Results and Discussionmentioning

confidence: 88%

From WCl₆ to WCl₂: Properties of Intermediate Fe–W–Cl Phases

Mos¹,

Castro²,

Indris

et al. 2015

Inorg. Chem.

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Phenomenological studies of WCl6 reduction with transition metal powders M = Mn, Fe, and Co have been recently reported. These reactions involve a series of reductive intercalation steps of M atoms into layered tungsten chloride arrangements, followed by exsolution of MCl2. In the series M = Fe, the presence of divalent iron is evidenced for Fe(x)WCl6, FeW2Cl10, Fe2W2Cl10, and (Fe,W)Cl2 by Mössbauer spectroscopy. Magnetic properties are reported. Bonding characteristics between tungsten atoms in edge-sharing [W2Cl10](n-) bioctahedra reveal that a double bond can be addressed to FeW2Cl10. A similar situation appears for Fe2W2Cl10, due to the localized and thus nonbonding character of the two electrons in the δ orbitals of this compound.

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Section: ■ Results and Discussionmentioning

confidence: 88%

From WCl₆ to WCl₂: Properties of Intermediate Fe–W–Cl Phases

Mos¹,

Castro²,

Indris

et al. 2015

Inorg. Chem.

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“…[29] Only recently,t he correct single-crystal structureo fb-WCl 6 was published, [27] whereas as tructure refinement based on powder X-ray data assumed WCl 6 to be isotypic to the wrong UCl 6 structure. [30] We carried out aq uantumc hemical structuralo ptimization on WCl 6 starting with wrong atom coordinates for W(2) (z = 0.52, DFT-PBE0-D3/TZVP level of theory). The optimization ends up in as tructure where z = 0.49041f or W(2), in full agreement with the revised UCl 6 structure reported here.…”

Section: Quantum Chemical Calculationsonr T-uclmentioning

confidence: 99%

A Revised Structure Model for the UCl₆ Structure Type, Novel Modifications of UCl₆ and UBr₅, and a Comment on the Modifications of Protactinium Pentabromides

Deubner

Rudel

Sachs

et al. 2019

Chemistry A European J

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The redetermination of the crystal structure of trigonal UCl6, which is the eponym for the UCl6 structure type, showed that certain atomic coordinates had been incorrectly reported. This led to noticeably different U−Cl distances within the octahedral UCl6 molecule (2.41 and 2.51 Å). Within the revised structure model presented here, which is based on single crystal data as well as quantum chemical calculations, all U−Cl distances are essentially equal within standard uncertainty (2.431(5), 2.437(5), and 2.439(6) Å). This room temperature modification, called rt‐UCl6, crystallizes in the trigonal space group Ptrue3‾ m1, No. 164, hP21, with a=10.907(2), c=5.9883(12) Å, V=616.9(2) Å3, Z=3 at T=253 K. A new low‐temperature (lt) modification of UCl6 is also presented that was obtained by cooling a single crystal of rt‐UCl6. The phase change occurs between 150 and 175 K. lt‐UCl6 crystallizes isotypic to a low‐temperature modification of SF6 in the monoclinic crystal system, space group C2/m, No. 12, mS42, with a=17.847(4), b=10.8347(18), c=6.2670(17) Å, β=96.68(2)°, V=1203.6(5) Å3, Z=6 at 100 K. The Cl anions form a close‐packed structure corresponding to the α‐Sm type with uranium atoms in the octahedral voids. During the synthesis of UBr5 a new modification was obtained that crystallizes in the triclinic crystal system, space group Ptrue1‾ , No. 2, aP36, with a=10.4021(6), b=11.1620(6), c=12.2942(7) Å, α=68.3340(10)°, β=69.6410(10)° and γ=89.5290(10)°, V=1231.84(12) Å3, Z=3 at T=100 K. In this structure the UBr5 units are dimerized to U2Br10 molecules. The Br anions also form a close‐packed structure of the α‐Sm type with adjacent uranium atoms in the octahedral voids. Comparisons of the crystal structures of the compounds MX5 (M=Pa, U; X=Cl, Br) show that the crystal structure of monoclinic α‐PaBr5 is probably not correct.

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“…A similar type of reduction, with metal incorporation into the structure of WCl 6 , has been reported for M x WCl 6 compounds with M = Mn, Fe, and Co. [5][6][7] Their crystal structures are also based on a hexagonal closest packing (hcp) arrangement of chloride ions and variable amounts of M ions occupying up to 1/3 of octahedral voids in every second interlayer.…”

Section: γ-Cu X Wclmentioning

confidence: 99%

“…Closely related crystal structures were reported for MW 2 Cl 10 (M = Mn, Fe, Co). [5][6][7] Both types of structures, Cu 2 W 2 Cl 10 and MW 2 Cl 10 , contain edge-sharing bioctahedra, which are well known from neutral [W 2 Cl 10 ] in WCl 5 , with a nonbonding W-W distance of 3.814(2) Å. [12] A study of the electronic situation of the W-W bonding within edge-sharing bioctahedra was reported for FeW 2 Cl 10 and Fe 2 W 2 Cl 10 .…”

Section: -Cu 2 W 2 CL 10mentioning

confidence: 99%

“…whereby tungsten is gradually reduced from the oxidation state +6 to +2. [4] More recently, the reduction of WCl 6 was explored with transition-metal powders such as Mn, Fe and Co. [5][6][7] Crystal structures of compounds appearing in these systems were refined by means of single-crystal and powder X-ray diffraction. More extensive studies were performed for compounds appearing in the Fe/W/Cl system, including electronic structure calculations, magnetic measurements, energy-dispersive X-ray spectroscopy (EDX) and Mössbauer spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

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Snap‐Shots of a Reduction Pathway: The Reaction of WCl₆ with Copper Powder

2016

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A combined differential scanning calorimetry (DSC)/X‐ray diffraction (XRD) methodology is used to search and identify compounds in the Cu/W/Cl system based on the successive reaction of WCl6 with copper powder. Thermal effects monitored by DSC are used to detect reaction pathways and phase formations of compounds. A series of five new and one already known compounds is discovered as crystalline phases in the Cu/W/Cl system and structurally characterized by XRD. The reaction of WCl6 with elemental copper begins at temperatures as low as 60 °C with the formation of crystalline powders of α‐CuxWCl6. Continuing reaction stages include the successive formation of crystalline phases β‐CuxWCl6, γ‐CuxWCl6, α‐Cu2W2Cl10, β‐Cu2W2Cl10, and Cu2[W6Cl14].

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Thermal Detection, Synthesis, and Structural Characterization of Compounds in the Co–W–Cl System

Cited by 10 publications

References 20 publications

From WCl₆ to WCl₂: Properties of Intermediate Fe–W–Cl Phases

From WCl₆ to WCl₂: Properties of Intermediate Fe–W–Cl Phases

A Revised Structure Model for the UCl₆ Structure Type, Novel Modifications of UCl₆ and UBr₅, and a Comment on the Modifications of Protactinium Pentabromides

Snap‐Shots of a Reduction Pathway: The Reaction of WCl₆ with Copper Powder

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Thermal Detection, Synthesis, and Structural Characterization of Compounds in the Co–W–Cl System

Cited by 10 publications

References 20 publications

From WCl6 to WCl2: Properties of Intermediate Fe–W–Cl Phases

From WCl6 to WCl2: Properties of Intermediate Fe–W–Cl Phases

A Revised Structure Model for the UCl6 Structure Type, Novel Modifications of UCl6 and UBr5, and a Comment on the Modifications of Protactinium Pentabromides

Snap‐Shots of a Reduction Pathway: The Reaction of WCl6 with Copper Powder

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From WCl₆ to WCl₂: Properties of Intermediate Fe–W–Cl Phases

From WCl₆ to WCl₂: Properties of Intermediate Fe–W–Cl Phases

A Revised Structure Model for the UCl₆ Structure Type, Novel Modifications of UCl₆ and UBr₅, and a Comment on the Modifications of Protactinium Pentabromides

Snap‐Shots of a Reduction Pathway: The Reaction of WCl₆ with Copper Powder