First examples of [Rh(Bident)(CO)(L)] complexes where L is N-donor ligand: Molecular structure of [Rh(8-Oxiquinolinato)(CO)(NH3)]

Selective oxidation of one (trans to N) carbonyl group in [Rh(8-Oxiquinolinato)(CO)2] with stoichiometric amount of Me3NO in MeCN produces a solution containing [Rh(Oxq)(CO)(Me3N)] and [Rh(Oxq)(CO)(MeCN)]. The ammonia complex, [Rh(Oxq)(CO)(NH3)], has been prepared by action of NH3 gas on this solution and characterized by IR, 1H and 13C NMR, and X-ray data. Spectral parameters, ν(CO), δ13C, and 1J(CRh), were measured in situ for a series of complexes [Rh(Oxq)(CO)(L)] (L = NAlk3, Py, PBu3, PPh3, P(OPh)3, C8H14) formed upon action of L on [Rh(Oxq)(CO)(NH3)] in THF. A new ν(CO) and δ13C based scale of σ-donor/π-acceptor properties of ligands L is proposed including NH3 and CO as the natural endpoints.

Graphical abstract[Rh(Oxq)(CO)(NH3)] has been prepared from [Rh(Oxq)(CO)2] via selective CO trans to N oxidation by Me3NO. A new scale of σ-donor/π-acceptor properties of ligands L is proposed based on the series [Rh(Oxq)(CO)(L)] including NH3 and CO as the natural endpoints.Figure optionsDownload full-size imageDownload as PowerPoint slide