Unexpected Formation of Metallofulleroids from Multicomponent Reactions, with Crystallographic and Computational Studies of the Cluster Motion. (20th October 2021)

• Record Type: Journal Article
• Authors: Li, Yanbang; Emge, Thomas J.; Moreno‐Vicente, Antonio; Kopcha, William P.; Sun, Yue; Mansoor, Iram F.; Lipke, Mark C.; Hall, Gene S.; Poblet, Josep M.; Rodríguez‐Fortea, Antonio; Zhang, Jianyuan
• Is Part Of: Angewandte Chemie. Volume 133:Number 48(2021)
• Page Start: 25473
• Page End: 25477
• Publication Date: 2021-10-20
• Subjects: cluster motion -- density functional calculations -- endohedral -- fullerenes -- multicomponent reaction; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202110881
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: New multicomponent reactions involving an isocyanide, terminal or internal alkynes, and endohedral metallofullerene (EMF) Lu3 N@C80 yield metallofulleroids which are characterized by mass‐spectrometry, HPLC, and multiple 1D and 2D NMR techniques. Single crystal studies revealed one ketenimine metallofulleroid has ordered Lu3 N cluster which is unusual for EMF monoadducts. Computational analysis, based on crystallographic data, confirm that the endohedral cluster motion is controlled by the position of the exohedral organic appendants. Our findings provide a new functionalization reaction for EMFs, and a potential facile approach to freeze the endohedral cluster motion at relatively high temperatures. Abstract : Various metallofulleroids were generated from a new isocyanide‐induced multicomponent reaction on clusterfullerenes. One ketenimine metallofulleroid has fixed Lu3 N cluster due to the presence of the nearby organic appendant from a neighbor molecule in the solid state.