Cationic (tripyrrinato)palladium(II) complexes |
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Authors: | Martin Bröring Carsten D Brandt Stephan Link |
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Institution: | Prof. Dr. Martin Bröring, Philipps-Universität Marburg, Fachbereich Chemie, Hans-Meerwein-Straße, D-35043 Marburg, Germany |
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Abstract: | The formation of cationic palladium(II)complexes TrpyPdII]+X− by salt metathesis of the respective trifluoroacetates with different salts of weakly coordinating anions X− was investigated. With non-hydrolizable counterions, cationic mono- and dinuclear complexes are observed depending on the nature of the anion X− and the solvent. The mononuclear cations, which are only formed with X = BArF, most probably carry a weakly bound molecule of dichloromethane at the fourth coordination site of PdII. When treated with diazoalkanes, only these are sufficiently reactive to form carbene complexes. Four- and five coordinate Lewis base adducts TrpyPdIIL]+ with L = CH3NC, tBuNH2, PMe3, PEt3 and PiPr3 and TrpyPdIIL2]+ with L = PMe3 were prepared from the mononuclear cations TrpyPdII]+BArF−. From structural studies it becomes apparent, that the formation of stable five coordinate PdII species is restricted to medium size ligands and depends on the delicate balance between the steric influence of L and the strain, which is induced on the TrpyPdII unit. |
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Keywords: | Tripyrrin Oligopyrroles Palladium X-ray structure determination Strain |
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