Rb<sub>4</sub>P<sub>6</sub>, a Phosphide with Planar Six‐Membered Phosphorus Rings

Schmettow, Walter; Lipka, Annegret; Schnering, Hans Georg̀ von

doi:10.1002/anie.197403451

Cited by 23 publications

(8 citation statements)

References 2 publications

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“…The reduction of elemental P to various (multi)cyclic P x y – ions has been extensively studied in the last decades and multiple reviews have been published . Structures with various polyphosphide ions include P 4 2– , P 5 – ions , and the P 6 4– unit in M 4 P 6 (M = K, Rb, Cs). Prominent polyphosphide clusters contain [P 7 3– ] and [P 11 3– ] ions .…”

Section: Resultsmentioning

confidence: 99%

Deca-Arylsamarocene: An Unusually Inert Sm(II) Sandwich Complex

Velzen

Harder

2018

Organometallics

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Samarocene sandwich complexes with superbulky penta-arylcyclopentadienyl ligands have been prepared and were structurally characterized: [(4-EtC 6 H 4 ) 5 C 5 ] 2 Sm (1) and [(4-iPrC 6 H 4 ) 5 C 5 ] 2 Sm (2). Analogous to the previously reported synthesis of [(4-nBuC 6 H 4 ) 5 C 5 ] 2 Sm, reaction of (DMAT) 2 Sm• (THF) 2 (DMAT = 2-Me 2 N-α-Me 3 Si-benzyl) and the appropriate Ar 5 C 5 H ligand gave 1 (66% yield) and 2 (59% yield). In contrast to the high reactivity of Cp* 2 Sm, complex 1 has been shown to be surprisingly stable toward reaction with a large variety of reagents. Even under forcing conditions, no reaction with N 2 , CO, CO 2 , pyrazine, trans-stilbene, pyridine, P 4 , and benzophenone was observed. Complex 1 reacts with cuminil ArC(O)C(O)Ar (Ar = 4-iPrC 6 H 4 ) to yield the Sm(III) sandwich complex [(4-EtC 6 H 4 ) 5 C 5 ] 2 Sm[ArC(O)C(O)Ar] (3), which could be isolated in 83% yield as a dark-red crystalline material. Complex 2 reacts with oxygen in the presence of phenazine to yield the bimetallic Sm(III) complex [(4-iPrC 6 H 4 ) 5 C 5 Sm(η 1 -phenazine)] 2 (μ:η 2 -η 2 -O 2 ) 2 (4) in 25% yield as dark-red crystals. The unusually high redox-stability of deca-arylsamarocenes originates from steric hindrance of the Sm metal center.

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Section: Resultsmentioning

confidence: 99%

Deca-Arylsamarocene: An Unusually Inert Sm(II) Sandwich Complex

Velzen

Harder

2018

Organometallics

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“…The quality of the crystals was controlled using precession photographs. The lattice parameters, the space group and the X-ray powder patterns indicated that Ca 4 Ag 2 [Si 6 ] is a filled-up derivative of α-K 4 & 2 P 6 (Rb 4 & 2 P 6 -type) [7], and that Ba 4 [6]. Accordingly, the structures were refined using the full matrix least-squares program SHELXTL-plus [13] Table 1.…”

Section: Structure Determinationmentioning

confidence: 99%

New Examples for the Unexpected Stability of the 10π-Electron Hückel Arene [Si6]10-

Gil

Carrillo‐Cabrera

Schultheiss

et al. 1999

Z. anorg. allg. Chem.

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The compounds Ba4Ag2Si6, Eu4Ag2Si6, and Ca4Ag2Si6, prepared from the elements at 1273 K (the components in inner corundum crucibles are enclosed in sealed quartz ampoules), are brittle semiconductors with silvery luster. They react slowly with acids liberating hydrogen. Ba4Ag2[Si6] and Eu4Ag2[Si6] crystallize like Ba4Li2[Si6] (space group Fddd (No. 70); a = 8.613 Å, b = 14.927 Å, c = 19.639 Å, and a = 8.420 Å, b = 14.585 Å, c = 17.864 Å, respectively), whereas Ca4Ag2[Si6] represents a new structure type (space group Fmmm (No. 69); a = 8.315 Å, b = 14.391 Å, c = 8.646 Å). The three compounds are Zintl phases with the formal charges M2+, Ag+ and [Si6]10–. The mean bond lengths d(Si–Si) = 2.335–2.381 Å in the 10π‐Hückel arene [Si6]10– as well as d(Ag–Si) = 2.464–2.595 Å vary with the size of the M2+ cations. The chemical bonding was analyzed in terms of the Electron Localization Function (ELF) and compared with the bonding in related systems (Ce4Co2Si6).

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“…The alkali hexaphosphides M 4 P 6 (M = Rb, Cs) were prepared according to procedures described in the literature from electrograde phosphorus (99.9999%, Hoechst) and distilled rubidium or caesium, respectively. 2,14,15 No other crystalline phases were detected via X-ray powder diffraction in glass capillaries with 0.5 mm diameter (Stoe Stadi P, germanium-monochromatized CuK a radiation with l = 1.540598 A ˚at room temperature). Due to heavy absorption of the X-ray beam in the case of the caesium compound, it was diluted with dried glass powder in the ratio of 1 : 10 for the powder diffraction experiment only.…”

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confidence: 99%