| Abstract
| - Aminophosphinites Ph2POCHPhCHMeNMeR (2a−c: a, R = H; b, R = Me; c, R = Ph2CH), prepared from the corresponding N-substituted (1S,2R)-ephedrines, cleanly react with[Rh(CO)2Cl]2 in benzene, affording complexes with P,N-chelating (3a, 4b) or monodentate(5b,c and 7c) ligands, depending on the steric bulk of the amino group and metal-to-ligandratio. Treatment of the chloro-bridged dimer 7c with AgClO4 in methylene chloride givesthe cationic complex 8c, containing not only P,N-chelating aminophosphinite but also a Phgroup of a N-diphenylmethyl fragment coordinated to Rh in an unusual η2 fashion. Formationof the chiral center at nitrogen occurs stereoselectively, and complexes 3a and 8c exist assingle diastereomers in the solid state and in solution. The structures of 3a and 8c wereestablished by single-crystal X-ray diffraction.
- Aminophosphinites 2a−c, prepared from the corresponding N-substituted ephedrines, cleanly react with [Rh(CO)2Cl]2, affording complexes with P,N-chelating or monodentate ligands. Treatment of the chloro-bridged dimer 7c with AgClO4 gives the cationic complex 8c, containing not only P,N-chelating aminophosphinite but also a Ph group of a N-(diphenylmethyl) fragment coordinated to Rh in an unusual η2 fashion. Formation of the chiral center at nitrogen in 3a and 8c occurs stereoselectively.
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