Wts. Huck et al., CONVERGENT AND DIVERGENT NONCOVALENT SYNTHESIS OF METALLODENDRIMERS, Journal of the American Chemical Society, 120(25), 1998, pp. 6240-6246
A new building block is constructed with one pyridine and two kinetica
lly inert complexed Pd(II) ions, for the controlled assembly of metall
odendrimers following either a convergent or a divergent route. The do
uble pincer ligand 8 was cyclopalladated with Pd[CH3CN](4)(BF4)(2) and
subsequently converted into the neutral bis-palladium chloride comple
x 3. The pyridine moiety of 3, that is covalently attached to the spac
er bridging the two pincer complexes, coordinates to activated palladi
um centers. Via a combination of pyridine(3) and cyano-based (2) build
ing blocks, dendrons up to generation three were assembled and charact
erized with H-1 NMR and FT-W spectroscopy and MALDI-TOF mass spectrome
try. These dendrons can coordinate through a cyano Ligand to an activa
ted nucleus 1 forming convergently assembled metallodendrimers. Altern
atively, building blacks 3 were used in the divergent assembly of more
stable metallodendrimers, because of the stronger coordination of pyr
idine compared to cyano ligands. The formation of metallodendrimers is
evidenced by IR and H-1 NMR spectroscopy and electro spray and MALDI-
TOF mass spectrometry.