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 co-ligand 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⋯sp³N–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 sp³P, sp³N, and sp²N ligating atoms have different electronic properties; ii) DMSO trans to sp³N strongly coordinates to Ru and is fixed by a PyC(6)H⋯OS 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.

中文翻译：

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轴向手性sp3P / sp3NH / sp2N结合的线性三齿配体的开发-Ru（II）配合物的fac选择性形成及其在酮加氢中的应用

一种新开发的手性线性三齿配体R-PN（H）N（R = H或Ph），在1,1'的C（2）和C（2'）位置具有Ph ₂ P和PyCH ₂ NH基团-联萘骨架，不带或带有C（3）-Ph取代基。C（3）-Ph的空间效应和DMSO共配体的电子效应实现了fac-RuCl ₂（Ph-PN（H）N）（dmso）和fac- [Ru（H- PN（H）N）（dmso）₃ ]（BF ₄）₂。借助以下优点构建了负责供体-受体双功能催化剂（DACat）的H–Ru⋯sp ³ N–H反应位点：i）sp ³ P，sp ³N和sp ² N连接原子具有不同的电子性质；ii）DMSO反式至sp ³ N强烈地与Ru配位，并被PyC（6）H = OS氢键固定；iii）单一的NH功能简化了DACat反应位点。协同作用已成功地实现了对空间需求的酮的不对称氢化。还研究了R-PN（H）N第一行过渡金属配合物的结构特征。