Poly phenyl nickel

With a view to preparing polymerizable complexes, thiophene-substituted nickel-dithiolene complexes [Ni(L)(L )] have been synthesized and used to prepare films by electrochemical polymerization. The features of the complexes and of the polymers depend on the number of thiophene substituents. In particular, the complex with four thiophene substituents (L = L = thpdt, 12) shows a narrower HOMO-LUMO gap as compared to complexes with two thiophene and two phenyl groups or four phenyl groups [Xmax, nm (e, M- cm- ) 976 (38800) L = L = 12 931 (37700) L = 12, L = 9, R = Ph 866 (30900) L = L = 9, R = Ph] and gave a polymer whose electrochemical features are similar to those of poly[l,2-di(2,5-thienylene)ethane], suggesting that similar extended chains are formed"". 

The nickel-mediated polymerization of p-hydroxy-substituted phenyl isocyanide 60 (R=H) afforded the corresponding poly(isocyanide) 65 in a 43% yield after 65 h at room temperature [81]. The polyhydroxylated polymer 65 was oxidized with NaOCl in THF (Scheme 43). The resultant black solid 66,... 

Asymmetrische Hydrierungen mit Platinmetallen Oder Raney-Nickel auf chiralen Tra-gern (Quarz8, Seidenfibroirr, Polyleucin10 u.a.) laufen selten mit mehr als 3% optischer Ausbeute ab, ahnliche Ergebnisse werden mit Palladium- und Rhodium-Katalysatoren er-zielt. Mit Palladium/Poly-L-leucin erhalt man z.B. aus a-Methyl-zimtsaure mehr R-(-)-2-Benzyl-propansaure bzw. aus a-Acetamino-zimtsaure mehr S-(-)-Phenyl-alanin (nach Hydrolyse)11. 

Arylthiophens and Di- and Poly-heterocycles. - The reaction of (201) with sulphur gave (202) in 45% yield. Treatment of the hydrazone (203) with PPA at 110°C gave (204), the structure of which was proven by desulphurization of a degradation product with Raney nickel. From the simple phenyl-hydrazone of ethyl 2-thienyl glyoxylate, (205) and (206) were obtained in a 7 3 ratio. Authentic (206) was prepared via the Friedel-Crafts reaction of... 

Copolymers of di5mes 8 with phenyl isocyanate afford poly(2-pyridones) 9. This copolymerization reaction uses nickel(O) complexes as initiators (63). 

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