Wydział Chemii

Katarzyna Wajda-Hermanowicz

Andrzej Kochel

Robert Wróbel

2018

Journal of Organometallic Chemistry

860

30-48

10.1016/j.jorganchem.2018.01.060

Naukowa

Angielski

Artykuł

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.

Rhodium complexes, Imino-phosphine ligands, X-ray crystallography, Oxidative addition, C-H activation

https://doi.org/10.1016/j.jorganchem.2018.01.060

http://www.elsevier.com