NHC-Derived Bis(amidiniophosphine) Ligands of Rh(I) Complexes: Versatile cis−trans Chelation Driven by an Interplay of Electrostatic and Orbital Effects - Archive ouverte HAL
Article Dans Une Revue Inorganic Chemistry Année : 2009

NHC-Derived Bis(amidiniophosphine) Ligands of Rh(I) Complexes: Versatile cis−trans Chelation Driven by an Interplay of Electrostatic and Orbital Effects

Yves Canac
Laure Vendier
Remi Chauvin

Résumé

The synthesis, structure, and electronic properties of a dicationic bis(amidiniophosphine) based on an o-phenylene bridge is described. In spite of the presence of two facing P-conjugated positive charges, this electron-poor diphosphine is shown to act as a versatile chelating ligand in a series of stable rhodium(I) complexes. IR analysis of a carbonyl complex showed that the σ-donating versus π-accepting character of the cationic ligand is comparable to that of a neutral trialkylphosphite. While the ligand is trans-chelating at a neutral Rh(I) center, it switches to cis-chelating at a cationic Rh+ center. This and other unusual geometrical features revealed by X-ray diffraction analyses are interpreted by a subtle interplay between antisymbiotic trans preference, electrostatic repulsion, and relative Lewis acidity of the transition metal centers.
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hal-03734869 , version 1 (21-07-2022)

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Yves Canac, Nathalie Debono, Laure Vendier, Remi Chauvin. NHC-Derived Bis(amidiniophosphine) Ligands of Rh(I) Complexes: Versatile cis−trans Chelation Driven by an Interplay of Electrostatic and Orbital Effects. Inorganic Chemistry, 2009, 48 (12), pp.5562-5568. ⟨10.1021/ic900348x⟩. ⟨hal-03734869⟩
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