Rhodium(I)-complexes of five new alkane-diyl based phosphine-aminophosphine (P,NP) type chiral ligands (Ph2PCH(CH3)(CH2)nCH(CH3)N(R1)PR22 (n = 0-2, R1 = Me, Et, iPr, R2 = Ph, Cy)) and a thioether-aminophosphine type compound ((S,S)-PhSCH(CH3)(CH2)CH(CH3)N(iPr)PPh2) have been synthesized. The investigation of the coordination chemistry of structurally analogous systems by NMR and IR spectroscopy and in one case by X-ray crystallography enabled the comparison of the effect of (i) the ligand backbone length, (ii) the N-substituent, (iii) the type of the coordinating functionality and (iv) the P-substituent in aminophosphine moiety on the stereo-electronic properties of the complexes. The novel Rh-compounds were tested in the asymmetric hydrogenation of a broad range of prochiral substrates including dimethyl itaconate, dehydroaminoacid derivatives and α,β-unsaturated enol ester phosphonates. Catalysts modified by the pentane-2,4-diyl based phosphine-aminophosphine ligands provided superior catalytic performance compared to the analogous butane- and hexane-diyl based systems and thioether containing compound. Most importantly, by the proper choice of the N-substituent outstanding enantioselectivities could be obtained in the asymmetric hydrogenation of acetamidocinnamic acid derivatives (up to 98% ee) and enol ester phosphonates (up to 97% ee).