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Novel dinuclear cyclometallated palladium complexes [{Pd(µ-NCO)(C⁁N)}2], containing asymmetric imidato –NCO– bridging units have been synthesised [C⁁N = 7,8-benzoquinolyl; –NCO– = succinimidate (1c), phthalimidate (2c) or maleimidate (3c)]. The reaction of these complexes, and the previously reported analogous imidate precursors containing a phenylazophenyl (1a–3a) or 2-pyridylphenyl (1b–3b) backbone, with tertiary phosphines provides novel mononuclear N-bonded imidate derivatives of the general formula [Pd(C⁁N)(imidate)(L)] [L = PPh3, P(4-F-C6H4)3 or P(4-MeO-C6H4)3]. The single crystal structures of [Pd(azb)(phthalimidate)(P(4-MeO-C6H4)3)] (9a) and [Pd(bzq)(phthalimidate)(PPh3)] (7c) have been established. Dinuclear complexes (1a–3a, 1b–3b, 1c–3c) demonstrate outstanding thermal stability in the solid-state, as shown by thermoanalytical techniques. A marked influence of …