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Redox-controlled chalcogen-bonding at tellurium: impact on Lewis acidity and chloride anion transport properties.

ABSTRACT: Our interests in the chemistry of atypical main group Lewis acids have led us to devise strategies that augment the affinity of chalcogen-bond donors for anionic guests. In this study, we describe the oxidative methylation of diaryltellurides as one such strategy along with its application to the synthesis of [Mes(C₆F₅)TeMe]⁺ and [(C₆F₅)₂TeMe]⁺ starting from Mes(C₆F₅)Te and (C₆F₅)₂Te, respectively. These new telluronium cations have been evaluated for their ability to complex and transport chloride anions across phospholipid bilayers. These studies show that, when compared to their neutral Te(ii) precursors, these Te(iv) cations display both higher Lewis acidity and transport activity. The positive attributes of these telluronium cations, which originate from a lowering of the tellurium-centered σ* orbitals and a deepening of the associated σ-holes, demonstrate that the redox state of the main group element provides a convenient handle over its chalcogen-bonding properties.

SUBMITTER: Zhou B

PROVIDER: S-EPMC8159482 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Redox-controlled chalcogen and pnictogen bonding: the case of a sulfonium/stibonium dication as a preanionophore for chloride anion transport.

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| S-EPMC8453555 | biostudies-literature

Carbonyl Activation by Selenium- and Tellurium-Based Chalcogen Bonding in a Michael Addition Reaction.

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| S-EPMC7027547 | biostudies-literature

Reply to a Comment on "The Nature of Chalcogen-Bonding-Type Tellurium-Nitrogen Interactions".

Project description:We reply to the comment by J.-M. Mewes, A. Hansen and S. Grimme (MHG), who challenged the accuracy of our re value for the N⋅⋅⋅Te distance in (C6 F5 )Te(CH2 )3 NMe2 determined by gas electron diffraction (GED). We conclusively demonstrate that MHG's quoted reference calculations are less accurate than they claim for solid state and gas phase. We show by higher level calculations, that we did not miss substantial contributions from open-chain conformers. Refinements on simulated scattering data show that such contributions would have had only an almost negligible effect on re (N⋅⋅⋅Te). MHG suggested the use of a H0-tuned GFN method for calculating vibrational corrections ra -re , but this did not change these values substantially. Alternative amplitude calculations using higher level analytic harmonic and numeric cubic force fields (PBE0-D3BJ/def2-TZVP) yield a GED value for re (N⋅⋅⋅Te)=2.852(25) Å that is well within the experimental error of our original value 2.918(31) Å but far from the 2.67(8) Å predicted by MHG. A now improved error estimation accounts for inaccuracies in the calculated auxiliary values. The gas/solid difference of the weak N⋅⋅⋅Te interaction is in a realistic range compared to other systems involving weak chemical interactions.

| S-EPMC8251573 | biostudies-literature

Is There a Single Ideal Parameter for Halogen-Bonding-Based Lewis Acidity?

Project description:Halogen-bond donors (halogen-based Lewis acids) have now found various applications in diverse fields of chemistry. The goal of this study was to identify a parameter obtainable from a single DFT calculation that reliably describes halogen-bonding strength (Lewis acidity). First, several DFT methods were benchmarked against the CCSD(T) CBS binding data of complexes of 17 carbon-based halogen-bond donors with chloride and ammonia as representative Lewis bases, which revealed M05-2X with a partially augmented def2-TZVP(D) basis set as the best model chemistry. The best single parameter to predict halogen-bonding strengths was the static ?-hole depth, but it still provided inaccurate predictions for a series of compounds. Thus, a more reliable parameter, ??* , has been developed through the linear combination of the ?-hole depth and the ?*(C-I) energy, which was further validated against neutral, cationic, halogen- and nitrogen-based halogen-bond donors with very good performance.

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The Nature of Chalcogen-Bonding-Type Tellurium-Nitrogen Interactions: A First Experimental Structure from the Gas Phase.

Project description:(C6 F5 )Te(CH2 )3 NMe2 (1), a perfluorophenyltellurium derivative capable of forming intramolecular N⋅⋅⋅Te interactions, was prepared and characterized. The donor-free reference substance (C6 F5 )TeMe (2) and the unsupported adduct (C6 F5 )(Me)Te⋅NMe2 Et (2 b) were studied in parallel. Molecular structures of 1, 2 and 2 b were determined by single-crystal X-ray diffraction and for 1 and 2 by gas-phase electron diffraction. The structure of 1 shows N⋅⋅⋅Te distances of 2.639(1) Å (solid) and 2.92(3) Å (gas). Ab initio plus NBO and QTAIM calculations show significant charge transfer effects within the N⋅⋅⋅Te interactions and indicate σ-hole interactions.

| S-EPMC7839716 | biostudies-literature

Anion Sensing through Redox-Modulated Fluorescent Halogen Bonding and Hydrogen Bonding Hosts.

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| S-EPMC10952190 | biostudies-literature

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