Renewable β-myrcene polymerization initiated by lutetium alkyl complexes ligated by imidophosphonamido ligand

β -imidophosphonamido ligated lutetium alkyl complex (NPN Dipp )Lu(CH 2 SiMe 3 ) 2 (THF) (NPN Dipp = Ph 2 P(NC 6 H 3 i Pr 2 -2,6) 2 ) with the activation of Al i Bu 3 and [Ph 3 C][B(C 6 F 5 ) 4 ] exhibited high catalytic activity, medium syndio-(rr = 66%) but remarkably high 3,4-regioselectivity for the polymerization of β -myrcene (MY). In sharp contrast, high isotactic 3,4-polymyrcene (PMY) (mm = 95%) was obtained by the precursor (NPN Et )Lu(CH 2 SiMe 3 ) 2 (THF) (NPN Et = PPh 2 (NC 6 H 3 i Pr 2 -2,6)(NC 6 H 4 -Et-2)) with less bulky substituents on the N -aryl ring.