Journal Article

PUBDB-2024-00580

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Confined Lewis Pairs: Investigation of the $X^− →$ Si$_{20}$ Interaction in Halogen‐Encapsulating Silafulleranes

Gasevic, T. ; Bamberg, M.Extern* ; Wicke, J. ; Bolte, M. ; Virovets, A.Extern* ; Lerner, H.-W. ; Grimme, S. ; Hansen, A. (Corresponding author) ; Wagner, M. (Corresponding author)Extern* ; Bursch, M. (Corresponding author)

2024
Wiley-VCH Weinheim

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Please use a persistent id in citations: doi:10.1002/anie.202314238  doi:10.3204/PUBDB-2024-00580

Abstract: A joint theoretical and experimental study on 32 endohedral silafullerane derivatives [X@Sii$_{20}$Yi$_{20}$] (X = F-I; Y = F-I, H, Me, Et) and Th-[Cl@Sii$_{20}$Hi$_{12}$Y$_8$] (Y = F-I) is presented. First, we evaluated the structure determining template effect of Cl in a systematic series of concave silapolyquinane model systems. Second, we investigated the X$^- \to$ Si$_{20}$ interaction energy (Eint) as a function of X and Y and found the largest Eint values for electron-withdrawing exohedral substituents Y. Given that X ions can be considered as Lewis bases and empty Sii$_{20}$Yi$_{20}$ clusters as Lewis acids, we classify our inseparable host–guest complexes [X@Sii$_{20}$Yi$_{20}$] as “confined Lewis pairs”. Third, $^{35}$Cl NMR spectroscopy proved to be highly diagnostic for an experimental assessment of the Cl$^- \to$ Sii$_{20}$ interaction as the paramagnetic shielding and, in turn, delta($^{35}$Cl) of the endohedral Cl ion correlate inversely with Eint. Finally, we disclose the synthesis of [PPN][Cl@Sii$_{20}$Yi$_{20}$](Y = Me, Et, Br) and provide a thorough characterization of these new silafulleranes.

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)

Research Program(s):

1. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
2. DFG project 506550642 - Siladodecahedrane: Untersuchungen zu Reaktivität, Bindungssituation und optoelektronischen Eigenschaften (506550642) (506550642)

Experiment(s):

1. PETRA Beamline P24 (PETRA III)

Appears in the scientific report 2024

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Database coverage:
; ; ; Clarivate Analytics Master Journal List ; Current Contents - Life Sciences ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; IF >= 15 ; JCR ; Nationallizenz ; SCOPUS ; Web of Science Core Collection

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