Polyether functionalised complexes

Compared to polymers, dendrimer architectures offer favourable conditions for fixation of catalytically active moieties thanks to their monodispersity, variability, structural regularity of the molecular scaffold, and numerous functionalisation possibilities. Catalytic units can be fixed - multiply if required - on the periphery, in the core of a dendrimer, or at the focal point of a dendron. If the dendrimers are suitably functionalised at the periphery, appropriate metal complexes can be directly attached to the surface of the molecule. In contrast, dendrimers functionalised in the core or at the focal point shield the catalytically active site through their shell structure in a targeted manner, for example to attain substrate selectivity in the case of reactants of different sizes [1]. The corresponding concepts of exodendral and endodendral fixation of catalysts were inttoduced in the context of functionalistion of carbosilane, polyether, and polyester dendrimers [2]. Exodendral fixation refers to attachment of the catalytic units to the... 

If this complex is sufficiently stable, then no further reaction occurs, and the polycondensation is obviated. However, as mentioned above, by using controlled monomer design, a variety of functionalised polymers (typical by with Mn = 10 000—30 000 and Mw/Mn = 2.0) can be synthesised polyethers [15,48 50], poly(thioether)s [48], polyesters [51,52], polycarbonates [53], polyketones [54], polysiloxanes [55-58], poly(carbosiloxane)s [59], poly(carbosilane)s [60], poly(carbodichlorosilane)s [61] and polymers with a conjugated % system [62]. 

The development of CTOwn ether functionalised imidazolinm salts starts from the consideration that it is possible to link one polyether chain with two imidazolinm nnits at the end points. Since a transition metal can coordinate two imidazoUnm salts in trans fashion [131,162,208], two of these (poly)ether fnnctionaUsed bis-carbenes can form a macrocychc crown ether type hgand system with two transition metal carbene linkages. In favonrable cases, a pincer type C,0,C ms-coordination to the same transition metal is conceivable, bnt may not be very likely when the great affinity of late transition metals to NHC ligands and the aversion of these same late transition metals to ether donor Ugands is taken into account. However, hanilabile stabilisation of transition metal complexes in catalytic processes can certainly be hoped for. 

Functionalisation of these templates with phosphine ligands, followed by complexation with Co or Pd precursors, led to the demonstration of remarkable dendritic effects on the activity and selectivity of the catalytic systems in the Pauson-Khand [63] and Heck reactions (Scheme 5) [64]. The advantage of the weakly coordinating polyether dendritic backbone, as compared with the coordinating dendritic backbones (e.g. polyamide), was demonstrated for the Heck reaction [65]. 

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