☆ 4.7 Article

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

INORGANIC CHEMISTRY (2009)

Journal

INORGANIC CHEMISTRY

Volume 48, Issue 12, Pages 5562-5568

Publisher

AMER CHEMICAL SOC

DOI: 10.1021/ic900348x

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Chemistry, Inorganic & Nuclear

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Abstract

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(l) complexes. IR analysis of a carbonyl complex showed that the a-donating versus pi-accepting character of the cationic ligand is comparable to that of a neutral trialkylphosphite. While the ligand is trans-chelating at a neutral Rh(l) 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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