New functionalized polynorbornenes have been obtained in good yields by vinylic copolymerization of norbornene with a (norbornenyl)SnBu(2)Cl monomer, catalyzed by [Ni(C(6)F(5))(2)(SbPh(3))(2)]. Subsequent functionalization produces a wide variety of polymers with different --SnBu(2)R groups (R=aryl, vinyl, alkynyl). The polymers can be used as R-transfer reagents in Stille couplings, thereby providing easy workup and separation of the polymeric tin byproducts from the coupling products. Tin contents of around 0.05 wt % are found in the Stille products. The stannylated polymers can be recycled and reused with good efficiency.

[Pd(Pf)(NCMe)(N−N)]BF4, (Pf = C6F5; N−N = ethylenediamine (en, 1), 2,2′-bipyridine (2), (2,6-iPrC6H3)NC(Me)C(Me)N(2,6-iPrC6H3) (diimine, 3)) are very efficient initiators of the radical polymerization of alkyl acrylates. Mechanistic studies reveal that the polymerization of methyl acrylate with 1 starts by the insertion of the monomer into the Pd−aryl bond of the catalyst to give [Pd{CH(CO2Me)CH2Pf}(N−N)(NCMe)]BF4, (N−N = en (5), diimine (7)). In contrast to the case for other cationic palladium complexes, the presence of a Pf group does not allow the formation of C,O-palladacycles with a suitable ring size. This allows complex 5 (or 7) to decompose not only by β-H elimination but also by homolytic cleavage of the Pd−C bond in the light. The radical species generated in this process start the polymerization. Complex 1 is also a very efficient catalyst in the vinyl addition polymerization of norbornene by an insertion mechanism. Complex 3 polymerizes ethylene. Although complexes 1 and 3 are versatile polymerization initiators by two different mechanisms, neither copolymerization of methyl acrylate and norbornene with 1 nor that of methyl acrylate and ethylene with 3 were successful, leading to either very low yields or mixtures of homopolymers.

Cleaner and environmentally more friendly cross-coupling reactions can be carried out by the use of polymers as supports. A lot of work has been devoted to attach palladium catalysts on polymers, so they can be easily separated from the reaction mixture and reused. An overview of the methods used for this purpose is given; they include the encapsulation of palladium complexes or palladium nanoparticles by polymers and the synthesis of polymeric ligands that coordinate to palladium. Polymer-supported reagents are also important

The Stille coupling can be carried out in a batch process using insoluble tin supports. The new type of support consists of stannylated polymers based on the vinylic polynorbornene skeleton that allow one to use a set‐up where the tin reagent is immobilized in a column. The immobilized stannylated polymeric reagent can be easily reused. The coupling products are thus obtained by a very simple work‐up procedure and have very low levels of tin contamination.

While most metallic elements across the Periodic Table form stable chelating β-diketiminato complexes, examples of Au(I) are conspicuous by their absence. We report here the reaction of K[HC(F(3)CC=NR)(2)] with AuCl(PPh(3)) which provides a rare example of a thermally stable gold(I) diketiminato complex, (Ph(3)P)Au[RN=C(CF(3))CH(CF(3))C=NR] [R = 3,5-C(6)H(3)(CF(3))(2)]. The complex is highly fluxional in solution but in the solid state adopts a U-conformation. By contrast, the analogous reaction of K[HC(F(3)CC=NR)(2)] with CuBr(PPh(3))(3) gives the rigid 18-electron chelate complex (Ph(3)P)(2)Cu[κ(2)-HC{(CF(3))C=NR}(2)].