Organometallics 2000, 19, 4025-4029
4025
P h osp h or u s-Con ta in in g Den d r im er s a n d Th eir
Tr a n sition Meta l Com p lexes a s Efficien t Recover a ble
Mu lticen ter Hom ogen eou s Ca ta lysts in Or ga n ic
Syn th esis
Vale´rie Maraval, Re´gis Laurent, Anne-Marie Caminade,* and
J ean-Pierre Majoral*
Laboratoire de Chimie de Coordination, CNRS, 205 Route de Narbonne,
31077 Toulouse Cedex 4, France
Received May 22, 2000
Metalladendrimers of generation 3 with either 24 terminal palladium or ruthenium
diphosphine complexes or one ruthenium diphosphine complex located at the core have been
found to be efficient, recoverable catalysts in three general organic reactions: Stille couplings,
Knoevenagel condensations, and Michael additions.
In tr od u ction
literature is concerned with the properties of metalla-
dendrimers as catalysts. The metal can be incorporated
at the core4 and more frequently on the surface.5
Recently dendrimer-encapsulated metal nanoparticules
were found to behave as efficient catalysts for the
hydrogenation of alkenes in aqueous solution6a or for
reactions in fluorous biphasic systems.6b Also, hydro-
formylation reactions with rhodium-complexed den-
drimers grafted on silica were successfully achieved.7
The search for an ideal catalyst that combines ad-
vantages of both homogeneous and heterogeneous ca-
talysis is at the center of many investigations. In that
sense metalladendrimers are emerging as a promising
class of compounds, as predicted by Tomalia and
Newkome1 and as demonstrated in a pioneering work
by van Koten et al. in 1994.2 This interest is due to the
properties of dendrimers: high solubility, high concen-
tration of easily accessible active sites, and easy separa-
tion by nanofiltration or precipitation, to name as a few.
We have previously prepared a variety of metalla-
dendrimers from the reaction of phosphorus-containing
dendrimers with various transition metal complexes.
The presence of ligands such as phosphanes and diphos-
phanes or PdN-PdS moieties either on the surface of
dendrimers or within the cascade structure allowed us
to isolate dendritic complexes incorporating metals such
as palladium, platinum, rhodium, ruthenium, gold, iron,
tungsten, or zirconium.8-17
Some reports describe the use of nonmetalated den-
drimers,3 but the majority of the work reported in the
* Corresponding authors. Fax: 33 5 61 55 30 03. E-mail: caminade@
lcc-toulouse.fr or majoral@lcc-toulouse.fr.
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10.1021/om0005607 CCC: $19.00 © 2000 American Chemical Society
Publication on Web 08/31/2000