Design, synthesis and properties of orthopalladated complexes: Proheterogeneous catalyst
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The reaction of multidentate ligand, 3-((E)-(2-((E)-4-aryldiazenyl)phenylimino)methyl)benzene-1,2-diol, H2L (H2L1, 1a; H2L2, 1b and H2L3, 1c) and (E)-2-((2-(aryldiazenyl)phenylamino)methyl)phenol, HA (HA1, 3a; HA2, 3b and HA3, 3c) [where H represents the dissociable protons upon complexation, and aryl groups of H2L and HA are phenyl for H2L1 and HA1, p-methylphenyl for H2L2 and HA2, and p-chlorophenyl for H2L3 and HA3], with Na2PdCl4 separately afforded orthometallated complexes [(L)Pd], (2a, 2b and 2c) and [(A)PdCl] (4a, 4b and 4c) respectively. In the case of [(L)Pd], the deprotonated L2− ligands bind palladium (II) in a tetradentate (C,N,N,O) fashion whereas in the case of [(A)PdCl], the deprotonated A ligands bind Pd(II) in tridentate (C,N,N) manner. X-ray structures of [(L1)Pd], (2a) and [(A1)PdCl] (4a) were determined to confirm the molecular structures. Both the complexes 4a and 5a exhibited catalytic activity toward Suzuki and Heck reactions. Conversion of [(A)PdCl] to its oxidized form upon ligand oxidation is reported.

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