ja309550z_si_001.pdf (62.58 MB)
Prato Reaction of M3N@Ih‑C80 (M = Sc, Lu, Y, Gd) with Reversible Isomerization
journal contribution
posted on 2012-12-19, 00:00 authored by Safwan Aroua, Yoko YamakoshiThe 1,3-dipolar cycloaddition of an azomethine ylide
(Prato reaction)
with M3N@Ih-C80 (denoted as M3N@C80; M = Sc,
Lu, Y, Gd) was carried out to obtain fulleropyrrolidinebis(carboxylic
acid) derivatives as scaffolds for the preparation of various functionalized
M3N@C80 materials. The formation of two monoadduct
isomers (the [6,6]- and [5,6]-adducts) were detected by HPLC and identified
by NMR and vis/NIR spectroscopies. In each Prato reaction with M3N@C80, the initial addition gave a [6,6]-adduct
of the Ih-C80 cage, and subsequently, a [5,6]-adduct was obtained by complete
or partial thermal isomerization via a rearrangement reaction. The
reaction rate of the latter thermal conversion of the adducts was
dependent on the size of the metal cluster inside C80,
and interestingly, in the reactions of Y3N@C80 and Gd3N@C80, this conversion was found to
be reversible for the first time. Detailed kinetic studies provided
the enthalpy and entropy barriers for the reactions of the adducts
of Lu3N@C80, Y3N@C80,
and Gd3N@C80. The utility of the obtained Prato
adducts was confirmed by preparation of a highly water-soluble Gd3N@C80 derivative.