Bis(phosphinophenyl)amido‐Ligated Binuclear Rare‐Earth Metal Complexes for Highly cis‐1,4‐Selective Polymerization of 1,3‐Conjugated Dienes

Abstract A series of binuclear rare‐earth metal complexes based on the ligands containing bis(phosphinophenyl)amido‐PNP unit are successfully synthesized. All the ligands and the corresponding binuclear complexes are fully characterized by NMR spectra ( 1 H, 13 C, and 31 P). In conjunction with [Ph 3 C][B(C 6 F 5 ) 4 ], all the binuclear complexes exhibited high catalytic activity and high cis ‐1,4‐selectivity (>99%) toward the polymerization of 1,3‐conjugated dienes (isoprene, β‐myrcene and β‐farnesene) with excellent livingness at room temperature or even 80 °C.