Synthesis and Characterization of Cobalttelluride Clusters with the Cubic Body-Centered Co9Te6(CO)8Core

Ebner, Alexander; Wächter, Joachim; Zabel, Manfred

doi:10.1023/b:jocl.0000027400.90257.91

Cited by 12 publications

(27 citation statements)

References 9 publications

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“…[4,5] These anions form in the reaction of [Cp* 2 NbTe 2 H] (Cp* = C 5 Me 5 ) with [Co 2 (CO) 8 ]. The appropriate cation is the very stable [Cp* 2 Nb(CO) 2 ] + .…”

Section: Introductionmentioning

confidence: 99%

“…The appropriate cation is the very stable [Cp* 2 Nb(CO) 2 ] + . A salt containing the hexacapped cubic [Co 9 Te 6 (CO) 8 ] 2-anion formed also in this reaction, but could be established only crystallographically (Figure 1). [5a] Electron-sponge properties were expected for this compound but could not yet be verified because of the lack of pure material.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…[7] A first hint for the formation of [Co 9 Te 6 (CO) 8 ] n-con- n-(a) and [3] n-(b) (n = 1,2) anions. [5,6] taining salts was obtained in the reaction of [Co 2 (CO) 8 ] with CH 3 Li-reduced [CpЈ 2 NbTe 2 H] (2), [8,9] which proceeds via highly reactive intermediates. [10] In this work we describe the preparation and supramolecular structures of the salts [PPN] n [3] {PPN = Ph 3 PNPPh 3 ; 3 = [Co 9 Te 6 (CO) 8 ]; n = 1,2}, which complete the product variety in the reaction sequence 2/CH 3 Li/ [Co 2 (CO) 8 ].…”

Section: Introductionmentioning

confidence: 99%

“…[5,6] taining salts was obtained in the reaction of [Co 2 (CO) 8 ] with CH 3 Li-reduced [CpЈ 2 NbTe 2 H] (2), [8,9] which proceeds via highly reactive intermediates. [10] In this work we describe the preparation and supramolecular structures of the salts [PPN] n [3] {PPN = Ph 3 PNPPh 3 ; 3 = [Co 9 Te 6 (CO) 8 ]; n = 1,2}, which complete the product variety in the reaction sequence 2/CH 3 Li/ [Co 2 (CO) 8 ]. We also report on the redox behavior of the [3] -anion, its magnetic properties and the electron structures of differently charged [3] n-(n = +1 to -5) clusters, and reactivity studies on salts containing [3] -are described.…”

Section: Introductionmentioning

confidence: 99%

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Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co₉Te₆(CO)₈ Clusters

et al. 2008

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International audienceExtended investigations of the reaction sequence [Cp′2Nb(Te2)H]/CH3Li/[Co2(CO)8] (Cp′ = tBuC5H4) led to the identification of Lin[3] {3 = [Co9Te6(CO)8]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN]n[3] (PPN = Ph3PNPPh3). These compounds form in the solid state columnar ([PPN][3]) or undulated 2D ([PPN]2[3]) supramolecular networks. Electrochemical studies of [Cp*2Nb(CO)2][3] (Cp* = C5Me5) or [Na(THF)6][3] revealed the presence of the redox couples [3]-/[3]2-/[3]3-/[3]4-/[3]5- regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [3]- containing salts form with PPh3AuCl or dppe decomposition products like [(PPh3)2Au][CoCl3PPh3] or [Co(CO)2dppe]2(μ-Te). A neutral cluster comprising the Co@Co8(μ4-Te)6 core formed in the reaction of [Cp*2Nb(CO)2][Co11Te7(CO)10] with PPh3AuCl, which gave [Co9Te6(CO)4(PPh3)4] (4) after oxidative cluster degradation and CO substitution. 4 was characterized by X-ray crystallography. DFT calculations carried out on all members of the [3]n (n = +1 to -5) family and on related species indicate that there is no significant Jahn-Teller distortion (and therefore no connectivity change) for any of the considered electron counts. Magnetic investigations on [PPN][3] show that the ground state of [3]- is a spin triplet with spins interacting antiferromagnetically in a 1D space

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“…[4,5] These anions form in the reaction of [Cp* 2 NbTe 2 H] (Cp* = C 5 Me 5 ) with [Co 2 (CO) 8 ]. The appropriate cation is the very stable [Cp* 2 Nb(CO) 2 ] + .…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co₉Te₆(CO)₈ Clusters

et al. 2008

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Atomically Precise Nanoclusters of Iron, Cobalt, and Nickel

Hayton

2023

Atomically Precise Nanochemistry

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Organo‐Gallium/Indium Chalcogenide Complexes of Copper(I): Molecular Structures and Thermal Decomposition to Ternary Semiconductors

Kluge

Biedermann

Holldorf

et al. 2013

Chemistry A European J

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Several organo-gallium/indium chalcogenide complexes of copper(I), stabilized by trialkylphosphines, were isolated, structurally characterized by using single-crystal X-ray diffraction, and investigated in thermolysis experiments. The syntheses with [E(Me3Si)2] (E=S, Se) as a starting material and a chalcogen source involve the elimination of volatile silyl acetate, silyl ethers, and methane from copper(I) acetate, and Group 13 metal trimethyl compounds, respectively. Chalcogenide complexes, according to the general formulas [(R3PCu)4(MeM)4E6] (1-6) and [(R3PCu)6(MeM)4M4S13] (7-9; with R=alkyl and M=Ga, In), and mixed chalcogenide-phenylchalcogenolate complexes [(iPr3PCuEPh)3(MeGaE)4] (10, 11) were isolated. The heavy atom cores of 1-6 consist of an octahedron of chalcogen atoms, interpenetrated by a cube of metal atoms. Depending on the steric demand of the phosphine ligands, two constitutions are observed; the metal atoms of the same element either forming tetrahedra, or parallelograms, respectively. This constitutional isomerism is further investigated by quantum chemical calculations. Complexes 7-9 contain a central sulfur atom, surrounded by two interpenetrating tetrahedra of Group 13 metal atoms, an octahedron of copper atoms, and an icosahedron of twelve outer sulfur atoms; the heavy atom framework of 10 and 11 is a "cut-out" of this structure. Thermolysis experiments include thermogravimetry measurements and subsequent Rietveld phase analysis of the residues by using powder X-ray diffraction. The homologous compounds 1, 3, 4, and 6 yield the respective crystalline ternary semiconductor material CuME2 at temperatures below 300 °C. Partial release of Me3 M during the thermolysis process results in excess copper in the residue and therefore in small amounts of additional binary copper chalcogenide phases or metallic CuM alloys. Compound 8 produces nanocrystalline CuGaS2 at about 300 °C.

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Synthesis and Characterization of Cobalttelluride Clusters with the Cubic Body-Centered Co₉Te₆(CO)₈Core

Cited by 12 publications

References 9 publications

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co₉Te₆(CO)₈ Clusters

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co₉Te₆(CO)₈ Clusters

Atomically Precise Nanoclusters of Iron, Cobalt, and Nickel

Organo‐Gallium/Indium Chalcogenide Complexes of Copper(I): Molecular Structures and Thermal Decomposition to Ternary Semiconductors

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Synthesis and Characterization of Cobalttelluride Clusters with the Cubic Body-Centered Co9Te6(CO)8Core

Cited by 12 publications

References 9 publications

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters

Atomically Precise Nanoclusters of Iron, Cobalt, and Nickel

Organo‐Gallium/Indium Chalcogenide Complexes of Copper(I): Molecular Structures and Thermal Decomposition to Ternary Semiconductors

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Synthesis and Characterization of Cobalttelluride Clusters with the Cubic Body-Centered Co₉Te₆(CO)₈Core

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co₉Te₆(CO)₈ Clusters

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co₉Te₆(CO)₈ Clusters