Kinetic and Donor Stabilization of Organotellurenyl Iodides and Azides

Klapötke, Thomas M.; Krumm, Burkhard; Nöth, Heinrich; Gálvez-Ruíz, Juan Carlos; Polborn, Kurt; Schwab, Ingo; Suter, Max

doi:10.1021/ic048219s

Cited by 47 publications

(40 citation statements)

References 43 publications

(95 reference statements)

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“…The alkyllithium reagent (PhMe 2 Si) 3 CLi, generated as described, [7] was treated with elemental selenium to give the selenolate (PhMe 2 Si) 3 CSeLi in a straightforward manner according to 77 Se NMR spectroscopy (in THF: δ = -63.3 ppm). The product mixture, which was obtained after hydrolysis and oxidation (exposure to air) of the selenolate, was surprisingly complex and, according to 77 Se NMR spectroscopy, consisted of several selenium-containing species.…”

Section: Resultsmentioning

confidence: 99%

“…[7] Here, the triselane (PhMe 2 Si) 3 CSeSeSeC(SiMe 2 Ph) 3 (1) is the main product, which can be explained by the bulkiness of the substituent, to stabilize selanes with increased chain lengths in the case of smaller chalcogens. The triselane 1 was separated from the mixture because of its lower solubility in diethyl ether.…”

Section: Resultsmentioning

confidence: 99%

“…[1] Chalcogen compounds containing the tris(trimethylsilyl)methyl group, (Me 3 Si) 3 C, have been prepared (sulfur, [2] selenium, [3][4][5] and tellurium [3,6] ). The introduction of such sterically demanding substituents at the heavier chalcogen elements has been a part of our research for the recent time, because they have been useful to stabilize or detect rather reactive species or intermediates in tellurium(II), [7] and selenium(II) azide chemistry. [8] The tris[dimethyl(phenyl)silyl]methyl group, (PhMe 2 Si) 3 C, is expected to have some increased shielding properties compared to the permethylated substituent.…”

Section: Introductionmentioning

confidence: 99%

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Formation of Unexpected Selenium‐Rich Compounds by Selenation of the Very Bulky (PhMe₂Si)₃CLi:s‐Tetraselenane, a Novel Polyseleno Heterocycle

et al. 2006

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The reaction of the highly crowded trisilylmethyllithium compound (PhMe2Si)3CLi with elemental selenium resulted in a variety of products, among them the triselane [(PhMe2Si)3CSe]2Se, the unexpected diselane [(PhMe2Si)2HCSe]2 and the novel heterocycle [(PhMe2Si)2CSeSe]2. The constitution of the latter could be elucidated from the NMR spectroscopic data and was confirmed by the crystal structure which displays the C2Se4 cycle in the twist form. Calculations were performed for the chair and twist conformers of the heterocycles [(H3Si)2CXX]2 (X = O, S, Se, Te, Po).

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Formation of Unexpected Selenium‐Rich Compounds by Selenation of the Very Bulky (PhMe₂Si)₃CLi:s‐Tetraselenane, a Novel Polyseleno Heterocycle

et al. 2006

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confidence: 94%

“…1 heteroatom-tellurium interactions and (TpsiTe) 2 for which the antiperiplanar conformation is imposed by the bulky substituents. 10 The Te1···Te2' distance in [Li(tmeda)] 2 2 (3.884 Å) is shorter than the sum of van der Waals radii for Te (4.12 Å).13 Moreover, the closely related neutral ditelluride 60 [( t BuNH)P(μ-N t Bu) 2 P(N t Bu)Te] 2 (4), which has a similar steric environment for the Te-Te linkage, exhibits a dihedral angle of −123.8° and a Te-Te bond length of 2.7204(9) Å (Fig. S1).…”

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A planar dianionic ditelluride and a cyclic tritelluride supported by P₂N₂rings

et al. 2013

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with a planar P 6 E 6 (E = S, Se) framework in which dichalcogenido (-E-E-) groups are linked by perpendicular 20 P V 2 N 2 rings. 5 The synthesis of these polychalcogen macrocycles involves the two-electron oxidation of the dianions 1a and 1b with I 2. We now report a detailed investigation of the oxidation of the tellurium analogue 1c that provides important insights into the initial oxidation process, as well as a notable difference in the 25 final outcome of the oxidation compared to that observed for 1a and 1b. Specifically, we have identified and structurally characterised (a) the dianionic ditelluride [Te(, with an unusual planar conformation, as the product of one-electron oxidation of 1c and (b) the cyclicas the result of further oxidation. DFT calculations were carried out in order to determine the reason(s) for the unusual planarity of the PTeTeP unit in the ditelluride 2.The oxidation of the dianion 1c (as its dilithium derivative)with a one-half molar equivalent of I 2 led to the isolation of extremely sensitive black crystals, which were identified by Xray crystallography as [Li(tmeda)] 2 2 (Eq. 1). 7 As depicted in Fig. 1 heteroatom-tellurium interactions and (TpsiTe) 2 for which the antiperiplanar conformation is imposed by the bulky substituents. 10 The Te1···Te2' distance in [Li(tmeda)] 2 2 (3.884 Å) is shorter than the sum of van der Waals radii for Te (4.12 Å).13 Moreover, the closely related neutral ditelluride 60 [( t BuNH)P(μ-N t Bu) 2 P(N t Bu)Te] 2 (4), which has a similar steric environment for the Te-Te linkage, exhibits a dihedral angle of −123.8° and a Te-Te bond length of 2.7204(9) Å (Fig. S1).14 In view of these observations, DFT calculations were carried out to probe whether the conformation of [Li(tmeda)] 2 2 is stabilized by 65 intramolecular Te1···Te2' secondary bonding interactions (3.884 Å). Satisfactory structures were obtained from geometry optimizations (PBE-D3, TZP, ZORA) for planar and synclinal models of [Li(tmeda)] 2 2 and 4 simplified using Me groups in lieu of t Bu. In both instances the planar conformations were higher in 70 energy, by 8 and 37 kJ mol -1 for the models of [Li(tmeda)] 2 2 and 4, respectively. Preferred P-Te-Te-P torsion angles are 98° for the former and 90° for the latter. The small difference of energy suggests that the conformation observed in the crystal structure of [Li(tmeda)] 2 2 is imposed by packing forces. Further analysis on 75 the electronic structures of the [Li(tmeda)] 2 2 models failed to identify a particular orbital interaction or contribution from dispersion that would help stabilize the antiperiplanar geometry.

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Theoretical and Computational Aspects of Organotellurium Compounds

Longo

Menezes

2011

Patai's Chemistry of Functional Groups

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Computational methods applied to organotellurium compounds are reviewed and some new systematic studies are provided for completeness. From the reviewed works, only those which have connections and/or insights into experimental data and observations are thoroughly considered. It is hoped that no expertise on computational quantum chemical methods will be needed, but a brief survey of computational methods and a list of acronyms are provided. Despite being applied to organotellurium compounds only in recent years, quantum chemical methods provide relevant information for comprehending, rationalizing and guiding experimental results and observations. However, there are further studies to be performed to ascertain the predictive features of these methods.

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Kinetic and Donor Stabilization of Organotellurenyl Iodides and Azides

Cited by 47 publications

References 43 publications

Formation of Unexpected Selenium‐Rich Compounds by Selenation of the Very Bulky (PhMe₂Si)₃CLi:s‐Tetraselenane, a Novel Polyseleno Heterocycle

Formation of Unexpected Selenium‐Rich Compounds by Selenation of the Very Bulky (PhMe₂Si)₃CLi:s‐Tetraselenane, a Novel Polyseleno Heterocycle

A planar dianionic ditelluride and a cyclic tritelluride supported by P₂N₂rings

Theoretical and Computational Aspects of Organotellurium Compounds

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Kinetic and Donor Stabilization of Organotellurenyl Iodides and Azides

Cited by 47 publications

References 43 publications

Formation of Unexpected Selenium‐Rich Compounds by Selenation of the Very Bulky (PhMe2Si)3CLi:s‐Tetraselenane, a Novel Polyseleno Heterocycle

Formation of Unexpected Selenium‐Rich Compounds by Selenation of the Very Bulky (PhMe2Si)3CLi:s‐Tetraselenane, a Novel Polyseleno Heterocycle

A planar dianionic ditelluride and a cyclic tritelluride supported by P2N2rings

Theoretical and Computational Aspects of Organotellurium Compounds

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Formation of Unexpected Selenium‐Rich Compounds by Selenation of the Very Bulky (PhMe₂Si)₃CLi:s‐Tetraselenane, a Novel Polyseleno Heterocycle

Formation of Unexpected Selenium‐Rich Compounds by Selenation of the Very Bulky (PhMe₂Si)₃CLi:s‐Tetraselenane, a Novel Polyseleno Heterocycle

A planar dianionic ditelluride and a cyclic tritelluride supported by P₂N₂rings