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Synthetic and spectroscopic characterization of Rh(I)-( S )-amino acid complexes with diphosphine and triphosphine ligands
Abstract:Reaction of Rh(η4-cod)(S)-amino-acidato] ((S)-amino acidate?=?(S)-O2C-CHR-NH2; cod?=?cycloocta-1,5-diene) with 1,2-bis(diphenylphosphino)ethane (dppe) affords the ionic Rh(dppe)2]{(S)-O2C-CHR-NH2} (R?=?Me, I; Ph, II) complexes. Reactions with 1,3-bis(diphenylphosphino)propane (dppp) or 2,2,2-tris(diphenylphosphinomethyl)ethane (triphos) give the neutral Rh(dppp){(S)-O2C-CHR-NH2}] (R?=?Me, III; Ph, IV) or Rh(η2-triphos){(S)-O2C-CHR-NH2}] (R?=?Me, V; Ph, VI) complexes. The complexes are characterized by elemental analysis, UV–Vis-, IR-, 1H/31P{1H} NMR- and mass-spectroscopy. Two molecules of dppe coordinate to the Rh(I) symmetrically by replacing both cod and (S)-amino acidate to give III. Only one molecule of dppp (or triphos) coordinate to the Rh(I) asymmetrically by replacing only cod to give IIIVI. Two diastereomeric Rh(I)-complexes are present in V and VI. The results further suggest that the ligands are arranged in a distorted square planar geometry around the Rh(I) centre. The use of triphos instead of dppe or dppp yields the same coordination sphere.
Keywords:Rh(η4-cod)-complexes  (S)-amino acids  Diphosphine and triphosphine  Diastereomers
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