Ruthenium-phosphines, polymeric, preparation

Ruthenium complexes of alkenes, dienes, or cyclodienes in oxidation states 0 and II are known. From a preparative view, an important class of compounds is the oligomeric or polymeric complexes of composition [(dialkene)RuX2] , which often serve as reagents for further transformations. Their synthesis is similar to the procedure that has been detailed for phosphine complexes that is, when RuCl3(aq) is refluxed in alcohol in the presence of the diene, an insoluble brown to orange oligomeric complex is deposited. However, the use of... 

This reaction has been modified for various conditions, such as the application of microwave irradiation and the application of phosphine-containing polymer prepared from the ruthenium-catalyzed ring-opening metathesis polymerization of the norbornene. Most importantly, this reaction has been extended to the coupling of primary or secondary alkyl halides with aryl, vinyl, and even alkyl halide (or tosylate) 31,3o,3p,3y,3dd,3nn,4v,4x,6... 

In order to explore the effect of the heteroatom in Fischer-carbene type ligands on the reactivity and thermal stability of ruthenium complexes, Grubbs et al. prepared and characterized a series of well-defined bis-phosphine 4-8, NHC imidazole (IMes) 9-12, and NHC imidazolidine (HglMes) 13 complexes (Figure 12.3) [17]. The exceptionally high stability of 8 at 55 C (20 days before half the complex was decomposed) could be explained by the chelation ofthe amide carbonyl to the ruthenium center. When tested in ROMP reactions, all Fischer carbene complexes demonstrated rapid and quantitative polymerization of norbornene (NBE) derivatives at room temperature, although the polymerization... 

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