N-H bond activation by palladium(ii) and copper(i) complexes featuring a reactive bidentate PN-ligand |
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Authors: | de Boer Sandra Y Gloaguen Yann Reek Joost N H Lutz Martin van der Vlugt Jarl Ivar |
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Affiliation: | Supramolecular & Homogeneous Catalysis Group, van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands. j.i.vandervlugt@uva.nl. |
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Abstract: | The first examples of reactivity at the backbone of a bidentate PN-ligand L1H relevant to N-H activation are described, leading to novel Pd(II) and Cu(I) amido complexes. Activation of the PN-ligand backbone led to selective dearomatization of the pyridyl ring structure. In the case of Pd(II), the intermediate could be efficiently stabilized using PMe(3). Selective N-H bond cleavage of e.g. trifluorosulfonylamide resulted in facile formation of mononuclear metal-amido species 2 and 4, which have been crystallographically characterized. Hydrogen-bonding dimerization is observed in these solid state structures. The results obtained with these structurally versatile and reactive scaffolds likely open up new avenues in cooperative catalysis. |
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