Phosphorylation of (S)-prolinol with P(NEt2)(3) was used to synthesize aminophosphite (2R,5S)-CH2(CH2)(2)NCHCH2OPNEt2, which was reacted with the corresponding amino alcohols to afford (2S,5R)- CH2(CH2)(2)NCHCH2OPO(CH2)(2)NMe2 (Va) and (2S,5R)-CH2(CH2)(2)NCHCH2OPO(CH2)(2)N(CH2)(4)CH2 (Vb). Reaction of Va with [Rh(CO)(2)Cl](2) (P/Rh = 1) yields the mononuclear chelate [Rh(CO)(P<^>N)Cl] (VIIa), while the analogous reaction with Vb results in a mixture of products with cis- and traps-orientation of the coordinated phosphorus and nitrogen atoms. Spectral characteristics of the products of coordination of ligands Va and Vb were compared with those for the binuclear reference complex [Rh(CO)(L)Cl](2) (VIII), where L is P-monodentate ligand (2S,5R)-CH2(CH2)(2)NCHCH2OPOEt2 (VI). The ligands and complexes were studied by IR, NMR, P-31 and C-13 spectroscopy, mass spectrometry, and elemental analysis methods. X-ray diffraction analysis of crystals VIII was performed.