Neue Selenolato‐verbrückte Cluster von Eisen und Nickel; die Strukturen von [Fe12(SePh)24] und [Na2(POPh3)6] [Ni20Se12(SeMe)10]

Fenske, Dieter; Fischer, Andreas

doi:10.1002/ange.19951070311

Cited by 19 publications

(6 citation statements)

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“…The wheels and ellipse are unusual examples of ferrous-based rings with a tetrahedral motif, of which [Fe 12 (SePh) 24 ] of Fenske and Fischer is the first documented example. [12] The sulfide cluster [Na 2 Fe 8À contains tetrahedral FeS 4 units, but it is a mixed valence compound, [13] as is [Fe 6 S 6 I 6 ]…”

Section: Dedicated To Roald Hoffmannmentioning

confidence: 99%

Ferrous Wheels, Ellipse [(tBu₃SiS)FeX]_n, and Cube [(tBu₃SiS)Fe(CCSitBu₃)]₄

2003

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The controlled aggregation of low-coordinate, transitionmetal complexes can lead to the generation of unusual oligomers, polymers or clusters. Inspired by Hoffmann's treatise on tetrahedral units as building blocks, [1,2] we sought "XMY" species as potential monomers for [M(m-X)(m-Y)] n , an oligomer or polymer based on the edge-connectivity of tetrahedra. Literature precedent [3] suggested the use of bulky thiolate and halide ligands as the m-X and m-Y linkages. [5,6] hence desymmetrization was viewed as one means toward oligomerization. FeX 2 (thf) 2 and one equivalent of tBu 3 SiSNa(thf) x (x = 1.4-1.7) were stirred for 18-24 h to provide yellow [(X 2 Fe)(m-SSitBu 3 ) 2 {FeX(thf)}]Na(thf) 4 (2 a, X = Cl, 74 %; 2 b, X= Br, 86 %) and cis-[{I(thf)Fe} 2 -(m-SSitBu 3 ) 2 ] (3, 75 %) upon isolation. The structures of 1, 2 b and 3 were determined by single-crystal X-ray crystallography, and quenching studies (D 2 O/DCl in D 3 COD) suggested that 2 a has the same thiolate:THF ratio (1:3.9) as 2 b. Elemental analyses were indeterminate, probably because of variable desolvation. Each complex has a m eff consistent with an S = 2 ground state (Evans' method [7] in [D 8 ]THF) and little orbital contribution: 2 a, 4.8 m B ; 2 b, 4.5 m B ; 3, 4.8 m B .If the solvent (THF) was removed after the above procedures, and the remaining solids were heated under vacuum (2 a, 808C, 1.5 h; 2 b, 798C, 2 h); 3, 117 8C, 5 h) and extracted into benzene, then desolvation and aggregation occurred, but not to the expected polymers. Instead, ferrous wheels [Fe(m-X)(m-SSitBu 3 )] n (C 6 H 6 ) m (X = Cl, n = 12, 4 a, 45 %;[8] X = Br, n = 12, 4 b, 72%) [9] and the ferrous ellipse [Fe(m-I)(m-SSitBu 3 )] 14 (C 6 H 6 ) m (5, 16%) [10] were isolated by crystallization. The structures of these complexes were determined by single-crystal X-ray crystallography, [11] but the benzene molecules of solvation, determined from quenching studies to be~0.5-1.0 equivalent per Fe atom, exhibited significant disorder, and were removed from the refinement by using PLATON methods.The chloride ferrous wheel, 4 a (Figure 1), packs in a tetragonal array of columns; the bromide derivative, 4 b, is isomorphous. The wheels consist of edge-shared tetrahedra, with the inner diameter comprises m-X ligands, and the periphery composed of m-SSitBu 3 linkages. The orientation of each shared tetrahedral edge alternates relative to the ring plane such that the three different transannular X···X separations are basically the same (4 a, 9.484 (29) av; 4 b, 9.483 (22) av) Because of the greater size of Br ion, the iron atoms in 4 b are slightly displaced towards the outside of the wheel relative to 4 a.The iodide ellipse, 5 (Figure 2) is constructed of tetrahedra linked on the perimeter by m-SSitBu 3 ligands, and internally by bridging iodides. Ellipse 5 also packs in columnar fashion, and has transannular d(I···I) of 11.101 (2), 11.499 (2), 12.402 (2) and 13.469 (2) . The tetrahedra form a ring with the iodides inside, despite the d(FeI) av = 2.672 (11) that is substantially long...

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Section: Dedicated To Roald Hoffmannmentioning

confidence: 99%

Ferrous Wheels, Ellipse [(tBu₃SiS)FeX]_n, and Cube [(tBu₃SiS)Fe(CCSitBu₃)]₄

2003

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“…The largest cyclic structure containing exclusively paramagnetic 3d metals is the Ni$\rm{^{II}_{24}}$ wheel reported by Winpenny and co‐workers,8 which is approximately an order of magnitude smaller that the giant wheels constructed from molybdate fragments by the Müller group;9 a Ni$\rm{^{II}_{12}}$ wheel is also known 10. Large, cyclic, polymetallic arrangements of other 3d metals, either unsupported or supported (by ions or molecules as guests), have been found for chromium( III ),11 manganese( III ),12 iron( II ),13 iron( III ),12, 14 cobalt( II ),15 and copper( II ) 16…”

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confidence: 95%

[{Fe(OMe)2[O2CC(OH)Ph2]}12]: Synthesis and Characterization of a New Member in the Family of Molecular Ferric Wheels with the Carboxylatobis(alkoxo) Bridging Unit

Raptopoulou

Tangoulis

Devlin

2002

Angew. Chem. Int. Ed.

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High-nuclearity transition-metal clusters continue to attract a great deal of interest, partly because of their fascinating physical properties and partly for the architectural beauty of their structures. An interesting subarea of 3d metal cluster chemistry is the small but growing family of molecules that have circular structures. Large cyclic polymetallic clusters are valued for their ability to mimic the properties of linear coordination polymers. [1] For example, theories developed for analyzing magnetically coupled ring systems have been extensively applied to calculate the thermodynamic properties of 1D materials. [2] Furthermore, the chemistry of circular molecular clusters is also associated with supramolecular chemistry. Anion and cation recognition provide the possibility of controlling the size of clusters. A representative example of this approach is the ability to address the synthesis of molecular rings by exploiting host ± guest interactions with alkali-metal cations, because alkali-metal cations are hosted by rings of different size. Thus, hexairon(iii) [3±5] and hexamanganese(iii) [6] complexes with cyclic M 6 O 12 cores can easily accommodate Li and Na ions, both in the solid state and in solution, whereas Cs ions require larger rings, such as M 8 O 16 . [5] Metal rings have excited mankind since mythological times. [7] The largest cyclic structure containing exclusively paramagnetic 3d metals is the Ni II 24 wheel reported by Winpenny and co-workers, [8] which is approximately an order of magnitude smaller that the giant wheels constructed from molybdate fragments by the M¸ller group; [9] a Ni II 12 wheel is also known. [10] Large, cyclic, polymetallic arrangements of other 3d metals, either unsupported or supported (by ions or molecules as guests), have been found for chromium(iii), [11] manganese(iii), [12] iron(ii), [13] iron(iii), [12, 14] cobalt(ii), [15] and copper(ii). [16] Restricting further discussion to the so-called ferric wheels with nuclearities equal to or higher than ten, the structurally characterized complexes that contain O-donor groups as bridging ligands are [{Fe(OMe) 2

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“…Generally, the metallacrowns can be synthesized using either multidentate ligands that bridge two metal ions4 or bridging chalcogen ligands, such as NaSR,5 NaSeR,6 and OR anions 7. We wanted to synthesize the bidentate ligand [NaS 2 COCH 2 CH 2 SCS 2 Na] from 2‐sulfanylethanol [HSCH 2 CH 2 OH] by reaction with carbon bisulfide in aqueous NaOH solution, and then treat this ligand with aqueous nickel sulfate to produce the polymer [NiS 2 COCH 2 CH 2 SCS 2 Ni] n .…”

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[Ni₆(SCH₂CH₂OH)₁₂]: A Double Crown [12]Metallacrown‐6 Nickel(II) Cluster

Jian

Jiao

et al. 2003

Angew Chem Int Ed

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Metallacrowns represent a new class of multinuclear clusters that are analogous to crown ethers in both structure and function. [1, 2] One may substitute heteroatoms, such as transition metals and nitrogen atoms, for the methylene carbon atoms of the parent ether complexes to form metallacrowns. There has been considerable interest in metallacrown chemistry owing to potential applications in chemically modified electrodes, anion-selective separation agents, liquid-crystal precursors, and magnetic materials. [3] Generally, the metallacrowns can be synthesized using either multidentate ligands that bridge two metal ions [4] or bridging chalcogen ligands, such as NaSR, [5] NaSeR, [6] and OR anions.[ (1), a novel [12]metallacrown-6 nickel cluster as shown by single-crystal X-ray diffraction. We repeated the experiment and were able to form this product in high yield. Herein we report the spontaneous self-assembly and crystal structure of compound 1 as well as investigations on its UV/Vis spectrum and thermal stability.The crystal lattice of compound 1 [8] is made up of a centrosymmetric [Ni 6 (SCH 2 CH 2 OH) 12 ] molecule (Figure 1). Each Ni atom is surrounded by four S atoms of the m 2 -SCH 2 CH 2 OH ligands in a distorted square-planar fashion. As a result, the edge-sharing NiS 4 planes connect to form a ring. The six nickel atoms approximately form a hexagon, with NiÀ Ni separations in the range of 2.9010(15)-2.9378(17) , vertex angles of 119.08(5)-121.38(5)8, and an average deviation of AE 0.001 from the best least-squares Ni 6 plane. The diameter of the ring, defined as the average distance between two opposing nickel atoms, is 5.84 . Two m 2 -S bridges

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Neue Selenolato‐verbrückte Cluster von Eisen und Nickel; die Strukturen von [Fe₁₂(SePh)₂₄] und [Na₂(POPh₃)₆] [Ni₂₀Se₁₂(SeMe)₁₀]

Cited by 19 publications

References 39 publications

Ferrous Wheels, Ellipse [(tBu₃SiS)FeX]_n, and Cube [(tBu₃SiS)Fe(CCSitBu₃)]₄

Ferrous Wheels, Ellipse [(tBu₃SiS)FeX]_n, and Cube [(tBu₃SiS)Fe(CCSitBu₃)]₄

[{Fe(OMe)2[O2CC(OH)Ph2]}12]: Synthesis and Characterization of a New Member in the Family of Molecular Ferric Wheels with the Carboxylatobis(alkoxo) Bridging Unit

[Ni₆(SCH₂CH₂OH)₁₂]: A Double Crown [12]Metallacrown‐6 Nickel(II) Cluster

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Neue Selenolato‐verbrückte Cluster von Eisen und Nickel; die Strukturen von [Fe12(SePh)24] und [Na2(POPh3)6] [Ni20Se12(SeMe)10]

Cited by 19 publications

References 39 publications

Ferrous Wheels, Ellipse [(tBu3SiS)FeX]n, and Cube [(tBu3SiS)Fe(CCSitBu3)]4

Ferrous Wheels, Ellipse [(tBu3SiS)FeX]n, and Cube [(tBu3SiS)Fe(CCSitBu3)]4

[{Fe(OMe)2[O2CC(OH)Ph2]}12]: Synthesis and Characterization of a New Member in the Family of Molecular Ferric Wheels with the Carboxylatobis(alkoxo) Bridging Unit

[Ni6(SCH2CH2OH)12]: A Double Crown [12]Metallacrown‐6 Nickel(II) Cluster

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Neue Selenolato‐verbrückte Cluster von Eisen und Nickel; die Strukturen von [Fe₁₂(SePh)₂₄] und [Na₂(POPh₃)₆] [Ni₂₀Se₁₂(SeMe)₁₀]

Ferrous Wheels, Ellipse [(tBu₃SiS)FeX]_n, and Cube [(tBu₃SiS)Fe(CCSitBu₃)]₄

Ferrous Wheels, Ellipse [(tBu₃SiS)FeX]_n, and Cube [(tBu₃SiS)Fe(CCSitBu₃)]₄

[Ni₆(SCH₂CH₂OH)₁₂]: A Double Crown [12]Metallacrown‐6 Nickel(II) Cluster