NOVEL DINUCLEAR CYCLOMETALLATED COMPLEXES OF PALLADIUM(II) DERIVED FROM N,N-(2,5-DICHLORO)TEREPHTHALYLIDENEBIS(CYCLOHEXYLAMINE) VIA OXIDATIVE ADDITION
1997
The oxidative addition of the bidentate Schiff base 1,4-(CyNCH)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).
Neue Dinukleare Cyclometallierte Komplexe von Palladium(II) durch oxidative Addition mit N,N-(2,5-dichloro)terephthalylidenbis(cyclohexylamin)
Die oxidative Addition der zweizahnigen Schiff-Base 1,4-(CyNCH)2-2,5-CI2C6H2 an Tris(dibenzylidenaceton)dipalladium(0) ergab den dicyclopalladierten Komplex [(Cl)PdN(Cy)C(H)C6H2C(H)N(Cy)Pd(Cl)]n (1). Die Umsetzung von 1 mit LiBr ergab das analoge Bromoderivat [(Br)PdN(Cy)C(H)C6H2C(H)N(Cy)Pd(Br)]n (2). Reaktionen von 1 oder 2 mit tertiaren Phosphinen in den Molverhaltnissen 1:2 bzw. 1:4 fuhrten zu den entsprechen den dinuklearen, cyclometallierten Komplexen [(L)(X)PdN(Cy)C(H)C6H2C(H)N(Cy)Pd(X)(L)] (3–9) und den nicht-cyclometallierten Komplexen [(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). Die Behandlung von 1 bzw. 2 mit Thalliumacetylacetonat fuhrte zu dem dinuklearen, cyclometallierten Komplex [(MeCOCHCOMe)PdN(Cy)C(H)C6H2C(H)N(Cy)Pd(MeCOCHCOMe)] (15).
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