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First examples of [Rh(Bident)(CO)(L)] complexes where L is N-donor ligand: Molecular structure of [Rh(8-Oxiquinolinato)(CO)(NH3)]
Authors:Yu.S. Varshavsky  M.R. Galding  S.N. Smirnov
Affiliation:a Institute of Chemistry, St. Petersburg State University, Petrodvorets, Universitetskii pr., 26, 198504 St. Petersburg, Russia
b Nesmeyanov Institute of Organoelement Compounds, Vavilova Street, 28, 117813 Moscow, Russia
Abstract: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.
Keywords:Rhodium(I) complexes   Carbonyl frequencies   13C chemical shifts   N-donors   Electronic parameters   Crystal structure
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