Synthesis, structure and electronic properties of octakis(.mu.3-sulfido)hexakis(triethylphosphine)hexatungsten as a tungsten analog of the molecular model for superconducting Chevrel phases

Saito, Taro; Yoshikawa, Akihiko; Yamagata, Tsuneaki; Imoto, Hideo; Unoura, Kei

doi:10.1021/ic00317a037

Cited by 81 publications

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“…[25][26][27][28][29][30][31][32] In order to appreciate the structure and bonding in 1, it is instructive to it compare to other members of the M 6 E 8 series. Arguably, the closest relative of 1 is Co 6 Te 8 -(PEt 3 ) 6 (2), the only other reported example of a molecular M 6 -Te 8 cluster.…”

Section: Discussionmentioning

confidence: 99%

Hexakis(triethylphosphine)octatelluridohexachromium and a molecule-based synthesis of chromium telluride, Cr3Te4

Hessen¹,

Siegrist²,

Palstra³

et al. 1993

Inorg. Chem.

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Cr6Te8 ( Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date: 01-05-2019Reprinted from Inorganic Chemistry, 1993, 32. (1) is formed by the reaction of TePEt 3 with either (Et 3 P) 2 Cr(allyl) 2 or Cr(2,4-dimethylpentadienyl) 2 . This compound can be converted to the extended inorganic solid state compound Cr 3 Te 4 by simple thermolysis. We have determined the structure of the title compound crystallographically (monoclinic; a = 13.076(5) Å, b = 21.194(7) Å, c = 23.694(7) Å, β = 105.21(5)°, V = 6276(10) Å 3 , Z = 4). The molecule is formed by a Cr 6 octahedron, a Te 8 cube, and a (PEt 3 ) 6 octahedron, all of which are concentric. We compare and contrast the structure and properties of the cluster with those of related solid-state compounds.

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Section: Discussionmentioning

confidence: 99%

Hexakis(triethylphosphine)octatelluridohexachromium and a molecule-based synthesis of chromium telluride, Cr3Te4

Hessen¹,

Siegrist²,

Palstra³

et al. 1993

Inorg. Chem.

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“…Previously, well-defined polynuclear clusters could be obtained from dimensional reduction of 3D-lattices. − Unfortunately, examples of dimensional reduction are limited in number, and to date, most current cluster syntheses rely on self-assembly reactions that lack control of the resulting cluster constitution, geometry, and local metal coordination environments. − Thus, reliable methods to assemble polynuclear clusters are required to rigorously undertake electronic structure evaluation of mixed valent clusters. Our lab and others − have reported the synthesis of clusters with varying nuclearity (three metals and higher) templated within a polynucleating ligand architecture to predispose the metal ions to bind in a specific manner to form the polynuclear aggregate.…”

Section: Introductionmentioning

confidence: 99%

Thermally Persistent High-Spin Ground States in Octahedral Iron Clusters

Sánchez

Betley

2018

J. Am. Chem. Soc.

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Chemical oxidation and reduction of the all-ferrous (HL)2Fe6 in THF affords isostructural, coordinatively unsaturated clusters of the type [(HL)2Fe6] n : [(HL)2Fe6][BArF24] (1, n = +1; where [BArF24]− = tetrakis[(3,5-trifluoromethyl)phenyl]borate), [Bu4N][(HL)2Fe6] (2a, n = −1), [P][(HL)2Fe6] (2b, n = −1; where [P]+ = tributyl(1,3-dioxolan-2-ylmethyl)phosphonium), and [Bu4N]2[(HL)2Fe6] (3, n = −2). Each member of the redox-transfer series was characterized by zero-field 57Fe Mössbauer spectroscopy, near-infrared spectroscopy, single-crystal X-ray crystallography, and magnetometry. Redox-directed trends are observed when comparing the structural metrics within the [Fe6] core. The metal octahedron [Fe6] decreases marginally in volume as the molecular reduction state increases as gauged by the Fe–Feavg distance varying from 2.608(11) Å (n = +1) to 2.573(3) (n = −2). In contrast, the mean Fe–N distances and ∠Fe–N–Fe angles correlate linearly with the [Fe6] oxidation level, or alternatively, the changes observed within the local Fe–N4 coordination planes vary linearly with the aggregate spin ground state. In general, as the spin ground state (S) increases, the Fe–N(H)avg distances also increase. The structural metric perturbations within the [Fe6] core and measured spin ground states were rationalized extending the previously proposed molecular orbital diagram derived for (HL)2Fe6. Chemical reduction of the (HL)2Fe6 cluster results in an abrupt increase in spin ground state from S = 6 for the all-ferrous cluster, to S = 19/2 in the monoanionic 2b and S = 11 for the dianionic 3. The observation of asymmetric intervalence charge transfer bands in 3 provides further evidence of the fully delocalized ground state observed by 57Fe Mössbauer spectroscopy for all species examined (1–3). For each of the clusters examined within the electron-transfer series, the observed spin ground states thermally persist to 300 K. In particular, the S = 11 in dianionic 3 and S = 19/2 in the monoanionic 2b represent the highest spin ground states isolated up to room temperature known to date. The increase in spin ground state results from population of the antibonding orbital band comprised of the Fe–N σ* interactions. As such, the thermally persistent ground states arise from population of the resultant single spin manifolds in accordance with Hund’s rules. The large spin ground states, indicative of strong ferromagnetic electronic alignment of the valence electrons, result from strong direct exchange electronic coupling mediated by Fe–Fe orbital overlap within the [Fe6] cores, equivalent to a strong double exchange magnetic coupling B for 3 that was calculated to be 309 cm–1.

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“…Although tungsten analogues of the Chevrel phases have never been prepared, molecular W 6 S 8 L 6 clusters are available. [17][18][19] In the pursuit of network structures with W 6 S 8 clusters as building blocks, we developed a high yield synthesis of W 6 S 8 (4-tbp) 6 (4-tbp = 4-tert-butylpyridine) starting from (Bu 4 N) 2 W 6 Cl 8 Cl 6 , 20 a procedure that was modified from McCarley's W 6 S 8 (pyridine) 6 cluster synthetic route. 18 Due to the ease of its preparation on a large scale (10 g) and its amenable properties, W 6 S 8 (4-tbp) 6 has become the key intermediate molecule in our cluster research.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and properties of Mo6S8(4-tert-butylpyridine)6 and related M6S8L6 cluster complexes (M = Mo, W)

Jin

Popp

Boettcher

et al. 2002

J. Chem. Soc., Dalton Trans.

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Octahedral molybdenum chalcogenide clusters are the building blocks of the well-known Chevrel phases. Although the synthesis of molecular Mo 6 S 8 L 6 (L = PEt 3 and pyridine) clusters has been previously reported, a high yield and larger scale synthetic procedure is needed to produce soluble Mo 6 S 8 L 6 (L = Lewis base ligand) clusters, so that they can be used as precursors for the construction of novel network structures. Using the previously developed W 6 S 8 (4tert-butylpyridine) 6 synthesis as a starting point, a facile, high yield (70%) synthesis of Mo 6 S 8 (4-tert-butylpyridine) 6 from (Bu 4 N) 2 Mo 6 Cl 8 Cl 6 was developed. This general sulfidation reaction scheme can be extended to the direct preparation of many M 6 S 8 L 6 (M = W, Mo; L = Lewis base ligand) complexes. Three Mo 6 S 8 L 6 complexes (L = PEt 3 , methylamine, 4,4Ј-bipyridine) were also prepared via ligand exchange reactions with Mo 6 S 8 (4-tert-butylpyridine) 6 . The above Mo 6 S 8 L 6 complexes were characterized and their reactivity was compared with their tungsten counterparts. Crystal structures were found for Mo 6 S 8 (4-tert-butylpyridine) 6 , Mo 6 S 8 (4,4Ј-bipyridine) 6 , and Mo 6 S 8 (methylamine) 6 .

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Synthesis, structure and electronic properties of octakis(.mu.3-sulfido)hexakis(triethylphosphine)hexatungsten as a tungsten analog of the molecular model for superconducting Chevrel phases

Cited by 81 publications

References 0 publications

Hexakis(triethylphosphine)octatelluridohexachromium and a molecule-based synthesis of chromium telluride, Cr3Te4

Hexakis(triethylphosphine)octatelluridohexachromium and a molecule-based synthesis of chromium telluride, Cr3Te4

Thermally Persistent High-Spin Ground States in Octahedral Iron Clusters

Synthesis, characterization and properties of Mo6S8(4-tert-butylpyridine)6 and related M6S8L6 cluster complexes (M = Mo, W)

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