Abstract
The coordination behavior of the heterofunctional phosphine ligand PPh2NH(2-Py), PPh2(o-C6H4)CH=N-(CH2)nPh (n = 0–3) and PPh2(o-C6H4)CH=N-(CH2)n-(2-Py) (n = 1 or 2) towards Rh(I) and Rh(III) are reported and examples of neutral and cationic complexes containing bi-dentate PˆN or tri-dentate PˆNˆN and NˆNˆC chelating modes of coordination are found. The synthesized complexes were characterized using different analytical and spectroscopic techniques including 1H, 13C{1H} and 31P{1H} NMR spectroscopy IR spectroscopy, ESI mass spectrometry and elemental analysis. The crystal structure of representative compounds has been determined by X-ray diffraction methods. The fluxional behavior in solution of the rhodium(I) complexes of the type [RhCl(CO)(PˆN)= has been investigated by NMR spectroscopy as well as the reactivity towards the oxidative-addition of MeI and I2. It was found that rhodium (III) complexes of the general formula [RhCl2(PˆN)2]Cl formed three of the five possible stereoisomers and that different solvents induced isomerization between these stereoisomers, indicating hemilability of the PˆN ligands.
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