Carbonyl rhodium(I) complexes containing (H)PNX (X = O or N) ligands deriving from natural aminoacid–amides. Synthesis, X-ray structure and spectroscopic characterization

The polyfunctional (H)PNX (X = O or N) ligands 1 and 2 react with [Rh(CO)2Cl]2 to give the corresponding chloro carbonyl complexes {Rh[κ2-(H)PN](CO)Cl} (1a and 2a), where the neutral ligands coordinate in a κ2-PN bidentate fashion, the square planar coordination being completed by the CO trans to N and the chloride trans to P. In chloroform solution 1a maintains its original structure, while 2a partially transforms into the cationic species {Rh[κ3-(H)PNO](CO)}Cl. The chloroform solutions of 1a and 2a react with AgPF6 to give the purely cationic species {Rh[κ3-(H)PNO](CO)}PF6 ([1a]+ and [2a]+), while addition of Et3N originates the neutral species {Rh[κ3-PNN′](CO)} (1b and 2b). All the complexes have been characterized by microanalysis, IR, 1H NMR as well as 31P{1H} NMR spectroscopy. The X-ray structures of ligand 1 and complex 1b are also reported.

Graphical abstractA series of new carbonyl Rh(I) complexes containing potentially tridentate chiral ligands have been obtained. The ligands can adopt a κ2-(H)PN, κ3-(H)PNO or κ3-PNN′ coordination mode, depending on the experimental conditions.Figure optionsDownload full-size imageDownload as PowerPoint slide