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• W1568482007 abstract "Three new Pd(II) complexes, i.e. [PdCl2L]2 (A), PdCl2L2 (B) and [Pd(μ-Cl)(L-H)]2 (C), each with two diethyl [α-(4-benzenazoanilino)-2-hydroxybenzyl]phosphonates (L) bound to either one or two palladium atoms, are synthesized and characterized by elemental analysis, by IR, UV–vis and solid-state 13C-NMR spectra. Complexes B and C are additionally characterized by 1H-, 13C- and 31P-NMR and electrospray mass spectrometry (ESMS) studies using dimethylformamide (DMF) as a solvent. In DMF solution adducts A and B undergo spontaneous rearrangement into the cyclopalladated complex C. Dynamic 1H-NMR study of this rearrangement as well as of the reactions of L with PdCl2 and Na2PdCl4 revealed a complex equilibrium in DMF solutions and enabled the formation mechanism of all involved species to be resolved. The complex A is immediately solvolyzed producing two molecules of intermediate M [PdCl2(L)(DMF)]. Complex M was also the first intermediate in the reaction of L with PdCl2. Once present in concentration above 10−5 mol dm−3 M dimerizes very fast into chloro-bridged dimer [PdCl(μ-Cl)(L)]2 (D) which undergoes cyclopalladation and converts into the complex C. The formation of C from the intermediate D is clearly demonstrated by the concentration dependence of the cyclopalladation reaction which has order greater than one. Chloride ions, released by cyclopalladation, react with D by splitting chloro-bridge and binding to metal atoms to produce byproduct [PdCl3(L)]− (T). The same species T are formed in the reaction of L with Na2PdCl4 whereby a chloride ion is replaced by the ligand L. The complex B undergoes similar, but slower, solvolytic reaction producing M and L while further reaction steps are identical as in the solvolysis of A." @default.
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• W1568482007 date "2003-12-01" @default.
• W1568482007 modified "2023-10-06" @default.
• W1568482007 title "Synthesis and characterisation of Pd(II) complexes with a derivative of aminoazobenzene" @default.
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• W1568482007 doi "https://doi.org/10.1016/j.jorganchem.2003.07.013" @default.
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