N-H bond activation by palladium(II) and copper(I) complexes featuring a reactive bidentate PN-ligand

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 i...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2012-01, Vol.41 (37), p.11276-11283
Main Authors: de Boer, Sandra Y, Gloaguen, Yann, Reek, Joost N H, Lutz, Martin, van der Vlugt, Jarl Ivar
Format: Article
Language:English
Subjects:
Activation
Backbone
Bonding
Catalysis
Cleavage
Dimerization
Ring structures
Scaffolds
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Summary: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.
ISSN:1477-9226
1477-9234
DOI:10.1039/c2dt31009k