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Article Dans Une Revue Organometallics Année : 2013

Electrostatic control of Pd2+ → Ag+ transmetalation of a bis-imidazoliophosphine ligand

Yves Canac
Christian Bijani
Rémi Chauvin

Résumé

Attempts to prepare a tetracationic Pd2+ complex of the dicationic bis-imidazoliophosphine ligand 1 by AgOTf-mediated chloride abstraction from the corresponding PdCl2 complex led to the observation of a Pd2+ ? Ag+ transmetalation giving a tricationic (1)Ag+ complex. The driving force of the process is attributed to the relaxation of electrostatic repulsion between the formal positive charges. VTP 31P NMR experiments in CD2Cl2 afford evidence of a fast equilibrium between the mononuclear (1)Ag+ complex and its dimer. The X-ray crystal structure of the latter reveals that bridging TfO? anions allow maintenance of the overall cohesion of the structure through attractive electrostatic interactions.
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hal-00993526 , version 1 (20-05-2014)

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Yves Canac, Christian Bijani, Carine Guyard-Duhayon, Rémi Chauvin. Electrostatic control of Pd2+ → Ag+ transmetalation of a bis-imidazoliophosphine ligand. Organometallics, 2013, 32 (15), pp.4054-4057. ⟨10.1021/om400602a⟩. ⟨hal-00993526⟩
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