Sc₃N@I_h-C₈₀ as a novel Lewis acid to trap abnormal N-heterocyclic carbenes: the unprecedented formation of a singly bonded [6,6,6]-adduct

Abstract

An unprecedented singly bonded [6,6,6]-adduct with an abnormal N-heterocyclic carbene structure, represents the first example of carbon-based Lewis acid–base pairs based on endohedral metallofullerenes.

Unexpected formation of 1,2- and 1,4-bismethoxyl Sc3N@Ih-C80 derivatives via regioselective anion addition: an unambiguous structural identification and mechanism study

“…Unexpectedly, BingelHirsch reactions of the paramagnetic M@C 82 (M=La, Y and so on) 6,24 also afforded singly-bonded adducts, and Lewis acid-base pairs of Sc 3 N@I h -C 80 /Lu 2 @C 82 and N-heterocyclic carbenes commonly bear the singly-bonded nature. 25,26 Additionally, the η 1 -complex of Y@C 2v (9)-C 82 Re(CO) 5 stands as an example with a metal-carbon single bond. 27 However, each of the above strategies requires a specific category of EMFs.…”

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C60 Fullerenes

“…have synthesized a series of supramolecular platinum(II) complexes in which the metal is attached to macrocycles containing pyrrolidine rings that are connected to C 60 . To our knowledge, NHC ligands bearing fullerene moieties have not been reported yet, apart from a recent study bearing C 80 …”

A crystalline anionic complex of scandium nitride endometallofullerene: experimental observation of single-bonded (Sc3N@Ih-C80−)2 dimers

“…1 shows that the Sc 3 N clusters have very similar orientations with respect to the intercage bonding sites in both dimers. In addition to the dimer of La 2 @C 80 , single-bonded derivatives of EMFs with I h -C 80 cages have been reported recently; the benzyl adduct of La 2 @C 80 is formed via a PHHJ carbon,17 the carbene adduct to Sc 3 N@C 80 is formed via a THJ carbon18 (note that the orientation of the Sc 3 N cluster inside the cage in the carbene adduct is very similar to that in the dimer reported in this work), and the Bingel addition to TiY 2 N@C 80 occurs at the PHHJ site 19. Recently, a single-bonded neutral PHHJ {Y@ C s (6)-C 82 } 2 dimer was found 16.…”