Chalcogen bonding in supramolecular structures, anion recognition, and catalysis

Kolb, Simon; Oliver, Gwyndaf A.; Werz, Daniel B.

doi:10.1016/b978-0-12-823144-9.00059-5

Cited by 8 publications

(6 citation statements)

References 185 publications

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“…For instance, we found that the SF 5 -CB in 55 survived PhLi under Weinreb amide arylation conditions in the synthesis of 59. [48] Furthermore, we were able to carry 60 through a chloropentafluorosulfanylation, ester hydrolysis, and amide bond formation sequence to access 61 in 23 % isolated yield over 3 steps without intermediate purification. While 54 is admittedly challenging to isolate without the aid of HPLC, we were able to demonstrate that the crude mixture can be telescoped through 2 additional steps, after which isomers of 61 proved separable.…”

Section: Forschungsartikelmentioning

confidence: 99%

Overcoming a Radical Polarity Mismatch in Strain‐Release Pentafluorosulfanylation of [1.1.0]Bicyclobutanes: An Entryway to Sulfone‐ and Carbonyl‐Containing SF₅‐Cyclobutanes

Kraemer,

Buldt,

Kong

et al. 2024

Angewandte Chemie

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The first assortment of achiral pentafluorosulfanylated cyclobutanes (SF5‐CBs) are now synthetically accessible through strain‐release functionalization of [1.1.0]bicyclobutanes (BCBs) using SF5Cl. Methods for both chloropentafluorosulfanylation and hydropentafluorosulfanylation of sulfone‐based BCBs are detailed herein, as well as proof‐of‐concept that the logic extends to tetrafluoro(aryl)sulfanylation, tetrafluoro(trifluoromethyl)sulfanylation, and three‐component pentafluorosulfanylation reactions. The methods presented enable isolation of both syn and anti isomers of SF5‐CBs, but we also demonstrate that this innate selectivity can be overridden in chloropentafluorosulfanylation; that is, an anti‐stereoselective variant of SF5Cl addition across sulfone‐based BCBs can be achieved by using inexpensive copper salt additives. Considering the SF5 group and CBs have been employed individually as nonclassical bioisosteres, structural aspects of these unique SF5‐CB “hybrid isosteres” were then contextualized using SC‐XRD. From a mechanistic standpoint, chloropentafluorosulfanylation ostensibly proceeds through a curious polarity mismatch addition of electrophilic SF5 radicals to the electrophilic sites of the BCBs. Upon examining carbonyl‐containing BCBs, we also observed rare instances whereby radical addition to the 1‐position of a BCB occurs. The nature of the key C(sp3)–SF5 bond formation step – among other mechanistic features of the methods we disclose – was investigated experimentally and with DFT calculations. Lastly, we demonstrate compatibility of SF5–CBs with various downstream functionalizations.

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Section: Forschungsartikelmentioning

confidence: 99%

Overcoming a Radical Polarity Mismatch in Strain‐Release Pentafluorosulfanylation of [1.1.0]Bicyclobutanes: An Entryway to Sulfone‐ and Carbonyl‐Containing SF₅‐Cyclobutanes

Kraemer,

Buldt,

Kong

et al. 2024

Angewandte Chemie

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“…It should be noted that compounds E/H, E/R and E/R', which are 10π-electron hetarenes, are widely used in contemporary chemistry and materials science due to a unique set of properties including high EAA, dualistic Lewis ambiphilicity; enhanced chromophoric/fluorophoric performances; redox ac-tivity; and a propensity to secondary bonding interactions with special emphasis on chalcogen bonding. [12][13][14][15][16][17][18][19][20] In some fundamental and applied aspects their EAA, highlighted by the formation of CT complexes and radical anions (RAs), plays the key role. [13,[18][19][20][21][22][23][24][25][26] The new effect described in this work clarifies some earlier unexplained findings, e. g. regarded to the EAA of C 6 R 6 benzene derivatives (R are the same as above).…”

Section: Introductionmentioning

confidence: 99%

Tuning Molecular Electron Affinities against Atomic Electronegativities by Spatial Expansion of a π‐System

et al. 2023

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2,1,3‐Benzochalcogenadiazoles C6R4N2E (E/R; E=S, Se, Te; R=H, F, Cl, Br, I) and C6H2R2N2E (E/R’; E=S, Se, Te; R=Br, I) are 10π‐electron hetarenes. By CV/EPR measurements, DFT calculations, and QTAIM and ELI‐D analyses, it is shown that their molecular electron affinities (EAs) increase with decreasing Allen electronegativities and electron affinities of the E and non‐hydrogen R (except Cl) atoms. DFT calculations for E/R+e⋅−→[E/R]⋅− electron capture reveal negative ΔG values numerically increasing with increasing atomic numbers of the E and R atoms; positive ΔS has a minor influence. It is suggested that the EA increase is caused by more effective charge/spin delocalization in the radical anions of heavier derivatives due to contributions from diffuse (a real‐space expanded) p‐AOs of the heavier E and R atoms; and that this counterintuitive effect might be of the general character.

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“…Amongst SBIs used for anions recognition and sensing, hydrogen, [21–23] halogen [24–31] and chalcogen [26,29–48] bondings ( HB , XB and ChB , respectively), are, perhaps, the most important; [29,42] in the case of chalcogens, they embrace also hypervalent derivatives, e. g. EF 5 (E=S, Se, Te) [49] . Combination of anion‐ and cation‐receipting moieties in a single scaffold is possible to provide cooperative ion‐pair recognition [30,50] …”

Section: Introductionmentioning

confidence: 99%

“…[4,[7][8][9][10][11][12][17][18][19]20] Amongst anions, halides [Hal] À (Hal = F, Cl, Br, I) are essentially important for living beings and their environment. [19] Amongst SBIs used for anions recognition and sensing, hydrogen, [21][22][23] halogen [24][25][26][27][28][29][30][31] and chalcogen [26,[29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] bondings (HB, XB and ChB, respectively), are, perhaps, the most important; [29,42] in the case of chalcogens, they embrace also hypervalent derivatives, e. g. EF 5 (E = S, Se, Te). [49] Combination of anion-and cation-receipting moieties in a single scaffold is possible to provide cooperative ion-pair recognition.…”

Section: Introductionmentioning

confidence: 99%

Halide Complexes of 5,6‐Dicyano‐2,1,3‐Benzoselenadiazole with 1 : 4 Stoichiometry: Cooperativity between Chalcogen and Hydrogen Bonding

Radiush,

Wang,

Chulanova

et al. 2023

ChemPlusChem

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The [M4–Hal]– (M = the title compound; Hal = Cl, Br, and I) complexes were isolated in the form of salts of [Et4N]+ cation and characterized by XRD, NMR, UV‐Vis, DFT, QTAIM, EDD, and EDA. Their stoichiometry is caused by a cooperative interplay of σ‐hole‐driven chalcogen (ChB) and hydrogen (HB) bondings. In the crystal, [M4–Hal]– are connected by the π‐hole‐driven ChB; overall, each [Hal]– is six‐coordinated. In the ChB, the electrostatic interaction dominates over orbital and dispersion interactions. In UV‐Vis spectra of the M + [Hal]– solutions, ChB‐typical and [Hal]–‐dependent charge‐transfer bands are present; they reflect orbital interactions and allow identification of the individual [Hal]–. However, the structural situation in the solutions is not entirely clear. Particularly, the UV‐Vis spectra of the solutions are different from the solid‐state spectra of the [Et4N]+[M4–Hal]–; very tentatively, species in the solutions are assigned [M–Hal]–. It is supposed that the formation of the [M4–Hal]– proceeds during the crystallization of the [Et4N]+[M4–Hal]–. Overall, M can be considered as a chromogenic receptor and prototype sensor of [Hal]–. The findings are also useful for crystal engineering and supramolecular chemistry.

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Chalcogen bonding in supramolecular structures, anion recognition, and catalysis

Cited by 8 publications

References 185 publications

Overcoming a Radical Polarity Mismatch in Strain‐Release Pentafluorosulfanylation of [1.1.0]Bicyclobutanes: An Entryway to Sulfone‐ and Carbonyl‐Containing SF₅‐Cyclobutanes

Overcoming a Radical Polarity Mismatch in Strain‐Release Pentafluorosulfanylation of [1.1.0]Bicyclobutanes: An Entryway to Sulfone‐ and Carbonyl‐Containing SF₅‐Cyclobutanes

Tuning Molecular Electron Affinities against Atomic Electronegativities by Spatial Expansion of a π‐System

Halide Complexes of 5,6‐Dicyano‐2,1,3‐Benzoselenadiazole with 1 : 4 Stoichiometry: Cooperativity between Chalcogen and Hydrogen Bonding

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Chalcogen bonding in supramolecular structures, anion recognition, and catalysis

Cited by 8 publications

References 185 publications

Overcoming a Radical Polarity Mismatch in Strain‐Release Pentafluorosulfanylation of [1.1.0]Bicyclobutanes: An Entryway to Sulfone‐ and Carbonyl‐Containing SF5‐Cyclobutanes

Overcoming a Radical Polarity Mismatch in Strain‐Release Pentafluorosulfanylation of [1.1.0]Bicyclobutanes: An Entryway to Sulfone‐ and Carbonyl‐Containing SF5‐Cyclobutanes

Tuning Molecular Electron Affinities against Atomic Electronegativities by Spatial Expansion of a π‐System

Halide Complexes of 5,6‐Dicyano‐2,1,3‐Benzoselenadiazole with 1 : 4 Stoichiometry: Cooperativity between Chalcogen and Hydrogen Bonding

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Overcoming a Radical Polarity Mismatch in Strain‐Release Pentafluorosulfanylation of [1.1.0]Bicyclobutanes: An Entryway to Sulfone‐ and Carbonyl‐Containing SF₅‐Cyclobutanes

Overcoming a Radical Polarity Mismatch in Strain‐Release Pentafluorosulfanylation of [1.1.0]Bicyclobutanes: An Entryway to Sulfone‐ and Carbonyl‐Containing SF₅‐Cyclobutanes