Novel dinuclear cyclometallated complexes of palladium(II) derived from N,N‐(2,5‐dichloro)terephthalylidenebis(cyclohexylamine) via oxidative addition

Abstract

AbstractThe oxidative addition of the bidentate Schiff base 1,4‐(CyNCH)2‐2,5‐Cl2C6H2 to tris(dibenzylideneacetone) dipalladium(0) gave the dicyclopalladated complex [(Cl)PdN(Cy)C(H)C6H2C(H)N(Cy)Pd(Cl)]n (1). Treatment of 1 with LiBr gave the analogous bromo derivative [(Br)PdN(Cy)C(H)C6H2C(H)N(Cy)Pd(Br)]n (2). Reaction of 1 or of 2 with tertiary phosphines in 1:2 or 1:4 molar ratios gave the dinuclear cyclometallated [(L)(X)PdN(Cy)C(H)C6H2C(H)N(Cy)Pd(X)(L)] (3–9), and non‐cyclometallated complexes [(L)2(X)PdN(Cy)C(H)C6H2C(H)N(Cy)Pd(X)(L)2] (10–14) (X = Cl, Br; L = PPh3, PEtPh2, PEt2Ph, PMePh2, as appropriate), respectively, Treatment of 1 or of 2 with thallium acetylacetonate gave the dinuclear cyclometallated complex [(MeCOCHCOMe)PdN(Cy)C(H)C6H2C(H)N(Cy)Pd(MeCOCHCOMe)] (15).