A newly developed chiral linear tridentate ligand, R-PN(H)N (R = H or Ph), possesses Ph2P and PyCH2NH groups at C(2) and C(2') positions of the 1,1'-binaphthyl skeleton without or with a C(3)-Ph substituent. The steric effect of C(3)-Ph and the electronic effect of the DMSO coligand realize the facial selective generation of fac-RuCl2(Ph-PN(H)N)(dmso) and fac-[Ru(H-PN(H)N)(dmso)3](BF4)2, respectively. Both an H-Ru-sp 3 N-H reaction site responsible for the donor-acceptor bifunctional catalyst (DACat) and a fence/plane chiral context were constructed by means of the following advantageous points: i) the sp 3 P, sp 3 N, and sp 2 N ligating atoms have different electronic properties; ii) DMSO trans to sp 3 N strongly coordinates to Ru and is fixed by a PyC(6)H-O=S hydrogen bond; and iii) the single NH function simplifies the DACat reaction site. The synergistic effect has led to success in the asymmetric hydrogenation of sterically demanding ketones. Structural characteristics of first-row transition metal complexes of R-PN(H)N have been also investigated.