Activation of C-H and C-Br bonds in cyclopalladation reactions of Schiff base ligands: Influence of the benzylidene ring substituents |
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Authors: | Leticia Naya Margarita López-Torres José M Vila Nina Gómez-Blanco |
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Institution: | a Departamento de Química Fundamental, Universidade da Coruña, 15071 A Coruña, Spain b Departamento de Química Inorgánica, Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spain |
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Abstract: | Reaction of Pd(AcO)2 with the Schiff base ligands 2-Br-4,5-(OCH2O)C6H2C(H) N(Cy) (a) and 4,5-(OCH2CH2)C6H3C(H) N(Cy) (b) leads to the cyclometallated compounds Pd{2-Br-4,5-(OCH2O)C6HC(H) N(Cy)-C6,N}(μ-O2CMe)]2 (1a) and Pd{4,5-(OCH2CH2)C6H2C(H) N(Cy)-C6,N}(μ-O2CMe)]2 (1b), respectively, via C-H activation. Treatment of a with Pd2(dba)3 gave Pd{4,5-(OCH2O)C6H2C(H) N(Cy)-C2,N}(μ-Br)]2 (6a), via C-Br activation. The metathesis reaction of 1a and 1b with aqueous sodium chloride gave the corresponding cyclopalladated dimers with bridging chloride ligands, 2a and 2b, respectively. Treatment of the halogen-bridged compounds with tertiary tri- and diphosphines in the appropriate molar ratio gave the mono and dinuclear compounds 3a-5a, 7a-9a and 3b-5b. The structure of compounds 3a, 4a, 5a, 8a, 2b, 3b and 5b has been determined by X-ray diffraction analysis. |
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Keywords: | Palladium Schiff base C-H activation C-Br activation Triphosphine Diphosphine |
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