Trans-chloro-(1-naphthyl)bis[tris-(4-methoxyphenyl)phosphane]-nickel(II) catalyzed Suzuki-Miyaura coupling of aryl chlorides with phenylboronic acid

• NiCl(MOTPP)2(1-naphthyl) was prepared and applied successfully.
• Excellent yields were achieved for the coupling of various aryl chlorides.
• The impact of MOTPP was studied by single crystal X-ray diffraction.
• The NiC and NiCl bonds in NiCl(MOTPP)2(1-naphthyl) were somewhat lengthened.
• MOTPP increased the electron density of Ni compared to TPP.

A readily accessible trans-chloro-(1-naphthyl)bis-[tris-(4-methoxyphenyl)phosphine]-nickel(II) [NiCl(MOTPP)2(1-naphthyl)] complex was prepared and applied successfully to the Suzuki-Miyaura coupling of aryl chlorides with phenylboronic acid. The pre-catalyst readily forms the catalytically active Ni(0) species in situ under mild conditions without an additional reducing reagent. The electron-rich methoxy moieties on the phosphine ligand may increase the electron density of Ni and thus accelerates the reaction rate of oxidative addition. Single crystal X-ray diffraction revealed the NiCl and NiC bonds were lengthened in comparison with those in NiCl(PPh3)2(1-naphthyl), presumably owing to the stronger electron donating ability of MOTPP, which would facilitate the oxidative addition step.

NiCl(MOTPP)2(1-naphthyl) could afford excellent yields (92–98%) within 1 h for the coupling of aryl chlorides bearing electron-withdrawing groups. Around 78–88% yields were observed for aryl chlorides with electron-donating or amino-substituents.Figure optionsDownload as PowerPoint slide