Large Telluroxane Bowls Connected by a Layer of Iodine Ions

Kirsten, Lars; Rodrigues, Jéssica Fonseca; Hagenbach, Adelheid; Springer, Andreas; Pineda, Nahum R.; Piquini, Paulo; Jungfer, Maximilian Roca; Lang, Ernesto Schulz; Abram, Ulrich

doi:10.1002/anie.202103700

Cited by 2 publications

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“…N C is au seful indicator to estimate the strength of contacts in compounds with "long-range interactions" and has been applied for the evaluation of compounds with halogen bonds by Metrangolo and Resnati. [16] Unlike the absolute values of the bond lengths,t his parameter allows ad irect comparison [36] Angewandte Chemie Forschungsartikel 15646 www.angewandte.de between "long-range" interactions with donor-acceptor pairs. This means for the compounds under study that the bonding forces for the "outer-sphere" Te À Ibonds are in the magnitude of those of the iodine atoms in the triiodide ions in (Me 3 NC 6 H 12 NMe 3 )I 3 .…”

Section: Resultsmentioning

confidence: 99%

“…Solid lines represent shorter bonds. [36] Angewandte Chemie (2). This results in as hift of the corresponding absorption from the visible part of the spectrum into the near UV range,a nd can explain the fact that compound 2 appears almost colorless,while the compounds 1 with phenyltellurium-centered half-shells have ab rownish color.M ore details are outlined in the Supporting Information.…”

Section: Forschungsartikelmentioning

confidence: 98%

“…As already described for the compounds 1 and 2,also the intact cluster [{(PhTe) 18 ). [36] Figure 5. View along the crystallographic c-axis of compound 2 depicting large hydrophobic voids between the cluster units.…”

Section: Forschungsartikelmentioning

confidence: 99%

“…Figure 1. a) Structure of 1a (the central pyridine ring is omitted for clarity) and b) top-view to one {(PhTe) 19 O 24 } 9+ half-shell of 1a with the central layer of iodine atoms and the central pyridine ring [36]. …”

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“…Dotted lines indicate TeÀO(blue) and TeI(purple) interactions larger than 3.220 and 3.636 , respectively (90 %ofthe sum of the van der Waals radii). Solid lines represent shorter bonds [36].…”

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Large Telluroxane Bowls Connected by a Layer of Iodine Ions

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Phenyltelluroxane clusters of the composition [{(PhTe) 19 O 24 } 2 I 18 (solv)] (1)a re formed during the hydrolysis of [PhTeI 3 ] 2 or the oxidation of various phenyltellurium(II) compounds with iodine under hydrolytic conditions.T he compounds consist of two half-spheres with a{(PhTe) 19 O 24 } 9+ network, which are connected by 18 iodine atoms.T he spherical clusters can accommodate solvent molecules such as pyridine or methanol in the center of two rings formed by iodine atoms.T he presence of other metal ions during the cluster formation results in as elective replacement of the central {PhTe} 3+ units of eachh alf-sphere as has been demonstrated with the isolation of [{(PhTe) 18 ({Ca-(H 2 O) 2 }O 24 } 2 I 16 ]( 2)a nd [{(PhTe) 18 ({Y(NO 3 )(H 2 O)}O 24 } 2 I 16 ] (3). Acrownether-like coordination by six oxygen atoms of the telluroxane network is found for the {Ca(H 2 O} 2 } 2+ and {Y-(NO 3 )(H 2 O)} 2+ building blocks.M ass spectrometric studies show that considerable amounts of the intact clusters are transferred to the gas phase without dissociation.

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confidence: 98%

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confidence: 99%

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Solvents and Ligands Matter: Structurally Variable Palladium and Nickel Clusters Assembled by Tridentate Selenium- and Tellurium-Containing Schiff Bases

2022

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Structurally variable organochalcogen clusters containing palladium(II) and nickel(II) ions were assembled starting from the salicylidene-substituted dichalcogenides (Y–C6H4–NCH–C6H4–OH)2 ({HLY}2, where Y = Se or Te), and palladium or nickel acetate. The tetrameric palladium clusters contain reduced chalcogenolato ligands {Y–C6H4–NCH–C6H4–O)}2– ({L′Y}2–, where Y = Se or Te), while the initially formed trimeric nickel clusters contain the intact, coordinated dichalcogenides. The palladium clusters have a general formula of [Pd4(L′Y)4] and represent the first examples of palladium complexes where both a gyrobifastigial and a pseudocubane arrangement of the central Pd4Y4 unit could be established with the same ligand, only depending on the solvents used for crystallization. Reduced density gradient (RDG) considerations based on density functional theory calculations suggest that the commonly referred to stabilizing chalcogen–palladium or palladium–palladium interactions for the two geometric arrangements are weak van der Waals contacts resulting from the contact of two nonbinding lone pairs. In the case of the pseudocubane arrangement, a repulsive steric effect, which is indicated by RDG analysis, is clearly supported by the cuplike distortions detected in the solid-state structure of the compound. In contrast to the reactions with palladium acetate, where the dichalcogenides were cleaved, during similar reactions with nickel acetate, the dichalcogenides remained intact and trimeric clusters of the composition [Ni-μ2-κ2-(Ni{κ5-LY}2)2-μ2-(OAc)2] (Y = Se, Te) were formed. Air oxidation and hydrolysis of [Ni-μ2-κ2-(Ni{κ5-LTe}2)2-μ2-(OAc)2] gave a rare example of a hexanuclear nickel cluster of the composition [Ni2-κ5-(Ni4-κ6-μ6-{(L′Te 2O3)(L′TeO2)2}2)-μ2-(H2O)2], which is composed of a well-defined framework consisting of tellurinic anhydride and tellurinate units, which proves the comparably higher oxidation sensitivity of the trinickel dichalcogenide complexes. Electron spray ionization mass spectrometry spectra of both the palladium and nickel clusters indicate that they show fluctional behavior with varying nuclearity in solution and can adopt multiple charge states especially because of the noninnocence of the chalcogen-based ligands. The complexes were fully characterized by spectroscopic methods, elemental analyses, and X-ray diffraction.

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Large Telluroxane Bowls Connected by a Layer of Iodine Ions

Cited by 2 publications

References 37 publications

Large Telluroxane Bowls Connected by a Layer of Iodine Ions

Large Telluroxane Bowls Connected by a Layer of Iodine Ions

Solvents and Ligands Matter: Structurally Variable Palladium and Nickel Clusters Assembled by Tridentate Selenium- and Tellurium-Containing Schiff Bases

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