Green catalysts with excellent performance in Cu-free
Sonogashira
coupling reactions can be prepared by the supramolecular decoration
of graphene surfaces with Pd(II) complexes. Here we report the synthesis,
characterization, and catalytic properties of new catalysts obtained
by the surface decoration of multiwalled carbon nanotubes (MWCNTs),
graphene (G), and graphene nanoplatelets (GNPTs) with Pd(II) complexes
of tetraaza-macrocyclic ligands bearing one or two anchor functionalities.
The decoration of these carbon surfaces takes place under environmentally
friendly conditions (water, room temperature, aerobic) in two steps:
(i) π–π stacking attachment of the ligand via electron-poor
anchor group 6-amino-3,4-dihydro-3-methyl-5-nitroso-4-oxo-pyrimidine
and (ii) Pd(II) coordination from PdCl
4
2–
. Ligands are more efficiently adsorbed on the flat surfaces of G
and GNPTs than on the curved surfaces of MWCNTs. All catalysts work
very efficiently under mild conditions (50 °C, aerobic, 7 h),
giving a similar high yield (90% or greater) in the coupling of iodobenzene
with phenylacetylene to form diphenylacetylene in one catalytic cycle,
but catalysts based on G and GNPTs (especially on GNPTs) provide greater
catalytic efficiency in reuse (four cycles). The study also revealed
that the active centers of the ligand-Pd type decorating the support
surfaces are much more efficient than the Pd(0) and PdCl
4
2–
centers sharing the same surfaces. All of the
results allow a better understanding of the structural factors to
be controlled in order to obtain an optimal efficiency from similar
catalysts based on graphene supports.