Metal complexes, post-polymerization

Synthesis of Block Copolymers by the Post-Polymerization Formation of Metal Complexes... 

Novel rathenium complexes with carborane ligands were employed as efficient catalysts for controlled polymer synthesis via Atom Transfer Radical Polymerization (ATRP) mechanism. The ability of carborane ligands to stabihze high oxidation states of transition metals allows the proposed catalysts to be more active than their cyclopentadienyl counterparts. The proposed catalysts do not reqnire additives such as aluminium alkoxides. It was shown that introdnction of amine additives into the polymerization mixture leads to a dramatic increase of polymerization rate leaving polymerization controlled. The living nature of polymerization was proved via post-polymerization and synthesis of block copolymers. 

It is the aim of this chapter to give an overview on both chemical and electrochemical techniques for producing metallic-particle-based CP nanocomposite materials and to outline the progress made in this field. The various synthetic approaches are organized in such a way as to present first those involving metal particle deposition in the course of polymerization, and subsequently post-polymerisation procedures that involve chemical, electrochemical, or adsorption processes (Figure 7.1). Well-established approaches, along with some newly developed techniques will be discussed, with special emphasis on those that are still underdeveloped. Synthesis of metal oxide particle-based CP composites (see e.g. [8]), as well as modification of CPs with transition-metal complexes (see e.g. [5]) remain outside the scope of this chapter. 

Post-polymerization functionalization has also been applied to the synthesis of terpyridine-modified polymers [ 126]. In a recent approach, Schubert and colleagues employed this method to prepare poly(pentafluorostyrene) with terpyridines in the side chains [127]. First, poly(pentafluorostyrene) with a narrow polydispersity index of just 1.08 was synthesized by nitroxide-mediated polymerization. In a second step, this polymer was converted with amine-functionalized terpyridine under microwave heating, selectively substituting the para-fluorines. Addition of iron(II) sulfate to a solution of the terpyridine-functionalized polymer in a mixture of chloroform and methanol leads to gelation at a polymer concentration of 33 g In another work, Schubert and coworkers prepared metal-cross-Iinked polymer networks from linear and tri-arm PEG precursors, both functionalized with terpyridine at their OH-termini [128]. Quantitative functionalization of these precursors was achieved by conversion of the hydroxy-functionalized PEG derivatives with 4-chloro-2,2 6, 2"-terpyridine under basic conditions. However, quantitative cross-linking with iron(II) chloride was not observed in methanol solutions, neither at room temperature nor at elevated temperature, but only a small quantity of cross-linked material precipitated from the solution. This observation was attributed to a strong tendency of the tri-arm PEG to form intramolecular complexes, acting as a chain stopper rather than as a cross-linker. 

Studies on borohydride complexes of post-transition metals are as follows. Theoretical calculations on M(BH4) (M = Cu, Ag, Au) at the ab initio level indicate that Cu(i) and Ag(i) congeners have tetrahydridoborate structures, while the gold complex adopts a hydridoborane structure HAu(BH3).37 MeZn 2 /-BH4) 30 is prepared by addition of B2H6 to ZnMe2 or MeZnCl and Li[BH4]. The X-ray structure shows a polymeric helical arrangement of ZnMe + and [BH4]- fragments—similar to Be(BH4) or H2Ga(BH4) 50.38... 

The modification of the AI13 species by substitution of secondary metal ions into the complex (311. rather than by addition polymerization (251. or post ion exchange (241. as originally proposed, adds a new and wide ranging versatility to the pillar itself. These materials may be expected to show not just a different catalytic reactivity, but changes in the way the pillars... 

The previous example illustrates that quantification on entirely polymeric systems is difficult to achieve and often requires elaborate post-modification steps. XPS analysis, however, can provide straightforward information on the presence of hetero-atoms from the graft polymer (e.g., phosphorus, nitrogen, and sulfur) if the substrate polymer does not contain these elements. Moreover, complexation of metal cations such as Fe ", Ni ", and Cu " can also be investigated. XPS is therefore complementary to other analysis techniques, such as UV spectroscopy and ATR-IR spectroscopy. 

Crown ethers and their derivatives have gained attention for their ability to form stable complexes with metal ions. The selective complexing properties of crown ethers towards metal ions have led recently to their incorporation into polymeric matrices. There are three main methods of crown ethers incorporation into polymer matrices. The first method is direct polymerization of the crown ether in a step-growth process, the second one is the polymerization through a chain-growth process, and the third one is post-functionalization of pre-formed polymers. 

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