Carbon Centered Trigonal Prismatic Tungsten Clusters [W6CCl18]n– (n = 1, 2) containing Copper(I) and Copper(II)

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

doi:10.1002/zaac.201500571

Cited by 6 publications

(3 citation statements)

References 27 publications

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“…Cu–Cl distances in α‐Cu x WCl 6 , β‐Cu x WCl 6 , and γ‐Cu x WCl 6 are d Cu–Cl = 2.28(1) Å, d Cu–Cl = 2.275(8) Å and d Cu–Cl = 2.274(1) Å. These values appear shorter than in other compounds with Cu + ions in tetrahedral surroundings such as in Cu[W 6 CCl 18 ] [ d Cu–Cl = 2.387(1) Å], CsCu 2 Cl 3 [ d Cu–Cl = 2.382(1) Å], and [N(CH 3 ) 4 ][Cu 2 Cl 3 ] [ d Cu–Cl = 2.406(1) Å] . At the same time these distances are longer than those reported for Cu 2+ ions in compounds such as Cs 2 CuCl 4 [ d Cu–Cl = 2.205(2) Å], [(CH 3 ) 4 N] 2 [CuCl 4 ] [ d Cu–Cl = 2.243.…”

Section: Resultsmentioning

confidence: 94%

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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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Section: Resultsmentioning

confidence: 94%

“…Recently, we have reported the reduction of WCl 6 with copper powder in the presence of a reactive carbon source leading to the trigonal‐prismatic carbon‐centered compound Cu[W 6 CCl 18 ] …”

Section: Introductionmentioning

confidence: 99%

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

2016

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“…Replacement of the triflate ligands proceeds upon reduction with cobaltocene in coordinating solvents such as pyridine and dimethylformamide, affording the cationic clusters, [W 6 (μ 6 -C)(μ-Cl) 12 (py) 6 ](OTf) 2 and [W 6 (μ 6 -C)(μ-Cl) 12 (dmf) 6 ](BF 4 ) 2 . Alternative high-temperature routes to [W 6 (μ 6 -C)(μ-Cl) 12 Cl 6 ] x − clusters comprise treatment of WCl 4 with Li 2 NCN (500 °C) or treatment of WCl 6 with C 6 Cl 6 and copper (700 °C) …”

Section: Strategies Toward Bridging Carbide Complexesmentioning

confidence: 99%

Transition Metal Carbide Complexes

Reinholdt

Bendix

2021

Chem. Rev.

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Carbide complexes remain a rare class of molecules. Their paucity does not reflect exceptional instability but is rather due to the generally narrow scope of synthetic procedures for constructing carbide complexes. The preparation of carbide complexes typically revolves around generating L n M−CE x fragments, followed by cleavage of the C−E bonds of the coordinated carbon-based ligands (the alternative being direct C atom transfer). Prime examples involve deoxygenation of carbonyl ligands and deprotonation of methyl ligands, but several other p-block fragments can be cleaved off to afford carbide ligands. This Review outlines synthetic strategies toward terminal carbide complexes, bridging carbide complexes, as well as carbide−carbonyl cluster complexes. It then surveys the reactivity of carbide complexes, covering stoichiometric reactions where the carbide ligands act as C 1 reagents, engage in cross-coupling reactions, and enact Fischer−Tropsch-like chemistry; in addition, we discuss carbide complexes in the context of catalysis. Finally, we examine spectroscopic features of carbide complexes, which helps to establish the presence of the carbide functionality and address its electronic structure.

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ChemInform Abstract: Carbon Centered Trigonal Prismatic Tungsten Clusters [W₆CCl₁₈]^n‐ (n = 1, 2) Containing Copper(I) and Copper(II).

2015

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Carbon Centered Trigonal Prismatic Tungsten Clusters [W 6CCl18]n-(n = 1, 2) Containing Copper(I) and Copper(II). -Cu[W 6CCl18] (I) is obtained by solid state reaction of -WCl 6, Cu, and C6Cl6 (evacuated silica tubes, 700 C, 2 h; heating and cooling rate of 2 K/min). Its crystal structure is resolved in the triclinic space group P1 (Z = 2, single crystal XRD) and further discussed in detail. The compound is stable in air and dissolves in organic solvents such as DMSO and acetone. Dissolution in DMSO yields Cu(dmso) 6[W 6CCl18] (II) which transforms to Cu(dmso)4[W6CCl18]2 (III) upon dissolution in acetone. (II) and (III) both contain C-centered trigonal prismatic tungsten clusters [W6CCl18] n-(n = 1, 2) and Jahn-Teller distorted octahedral Cu(II) ions (space group C2/c, Z = 4 and P1, Z = 1, respectively). The presence of interstitial carbon in the cluster is confirmed by NMR. -(MOS, A.; STROEBELE, M.; MEYER*, H.-J.; Z. Anorg. Allg. Chem. 641 (2015) 12-13, 2245-2249, http://dx.doi.org/10.1002/zaac.201500571 ; Abt. Festkoerperchem. Theor. Anorg.

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Carbon Centered Trigonal Prismatic Tungsten Clusters [W₆CCl₁₈]^n– (n = 1, 2) containing Copper(I) and Copper(II)

Cited by 6 publications

References 27 publications

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

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

Transition Metal Carbide Complexes

ChemInform Abstract: Carbon Centered Trigonal Prismatic Tungsten Clusters [W₆CCl₁₈]^n‐ (n = 1, 2) Containing Copper(I) and Copper(II).

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Carbon Centered Trigonal Prismatic Tungsten Clusters [W6CCl18]n– (n = 1, 2) containing Copper(I) and Copper(II)

Cited by 6 publications

References 27 publications

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

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

Transition Metal Carbide Complexes

ChemInform Abstract: Carbon Centered Trigonal Prismatic Tungsten Clusters [W6CCl18]n‐ (n = 1, 2) Containing Copper(I) and Copper(II).

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Carbon Centered Trigonal Prismatic Tungsten Clusters [W₆CCl₁₈]^n– (n = 1, 2) containing Copper(I) and Copper(II)

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

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

ChemInform Abstract: Carbon Centered Trigonal Prismatic Tungsten Clusters [W₆CCl₁₈]^n‐ (n = 1, 2) Containing Copper(I) and Copper(II).