Ru(II)‐PBTNNXN complex bearing functional 2‐(pyridin‐2‐yl)benzo[d]thiazole ligand catalyzed α‐alkylation of nitriles with alcohols

• Published in: Applied organometallic chemistry 2020-04, Vol.34 (4), p.n/a
• Main Authors: Huang, Shuang, Hong, Xi, Sun, Yong, Cui, He‐Zhen, Zhou, Quan, Lin, Yue‐Jian, Hou, Xiu‐Feng
• Format: Article
• Language: English
• Subjects: 2‐(pyridin‐2‐yl)benzo[d]thiazole (PBT); alcoholsnitrilesRu (II) complex; α‐alkylation
• ISSN: 0268-2605; 1099-0739
• DOI: 10.1002/aoc.5451

Six tridentate NNN ligand precursors derived from 2‐(pyridin‐2‐yl)benzo[d]thiazole(PBT) with different linkers, PBTNNXN (X = NH, NMe, O, S) (1a–1f), have been successfully prepared. The electronic properties of PBTNNXN ligands are well tunable by differing linkers between PBT skeleton and the pyridine ring, and/or by introducing electron‐donating/withdrawing groups on the pyridine ring (R = OMe or F). The ligand precursors and representative complexes Ru (PBTNNNHN)Cl2(PPh3) (2a), Ru (PBTNNNMeN)Cl2(PPh3) (2b), and Ru (PBTNNSN)Cl2(PPh3) (2f) have been characterized by NMR spectroscopy, high‐resolution mass spectroscopy, and Fourier transform infrared (FT‐IR). The molecular structures of 1f, 2a, and 2f have been determined by X‐ray diffraction study. The results indicate that PBTNNNHN ligand in the complex presented coplanar with two five‐membered chelating rings. It should be noted that 2a featuring a NH group exhibits superior performance compared to those with other linkers (such as NMe, O, or S). A variety of heterocyclic and aromatic nitriles with aromatic and aliphatic alcohols have been explored in α‐alkylation for good to excellent yields. Based on kinetic experiments and mechanistic studies, a proposed mechanism was put forward. Ru‐H species and benzaldehyde, which was oxidized from benzyl alcohol, were detected in the catalytic cycle. Sixtridentate NNN ligands derived from 2‐(pyridin‐2‐yl)benzo[d]thiazole‐pyridine with different linkers, PBTNNXN (X = NH, NMe, O, S), and three complexes Ru (PBTNNNHN)Cl2(PPh3) (2a), Ru (PBTNNNMeN)Cl2(PPh3) (2b), and Ru (PBTNNSN)Cl2(PPh3) (2f) were prepared. The Ru complex 2a containing NH linker exhibited superior catalytic activity in the α‐alkylation of nitriles with alcohols and the yield was up to 98%.