Highly Active Iminopyridyl Iron-Based Catalysts for the Polymerization of Isoprene

A series of iminopyridyl-based ligands, 6-[(Ar)N=C(R)]-2-C₆H₅N [(Ar = 2,6-Me₂-C₆H₃, R = Me (L1); Ar = 2,6-Pr₂-C₆H₃, R = Me (L2); Ar = 2,6-Me₂-C₆H₃, R = H (L3); Ar = 2,6-Pr₂-C₆H₃, R = H (L4); Ar = 3,5-(CF₃)₂-C₆H₃, R = Me (L5); Ar = C₆F₅, R = Me (L6)], and their corresponding iron (II) complexes were developed to investigate their application in the controlled coordinative polymerization of isoprene. The modulation of steric and electronic properties within this family of ligands/pre-catalysts has shown to influence the stereo-selectivity and activity of the polymerization of isoprene after activation. Upon activation with various co-catalysts such as AlBu₃/[Ph₃C][B(C₆F₅)₄], AlEt₃/[Ph₃C][B(C₆F₅)₄] or MAO, the resulting catalysts produced polyisoprenes with an excellent conversion (>99% of 500-5000 equiv.) within less than 1 h (TOF > 500 h^-1) and having a variety of stereo-/regio-regularities. The presence of electron-donating and withdrawing groups drastically impacted the activity and the stereoselectivity of the catalysts during the course of the polymerization of isoprene. When activated with AlBu₃/[Ph₃C][B(C₆F₅)₄], the complexes {6-[(2,6-Me₂-C₆H₃)N=C(Me)]-2-C₆H₅N}FeCl₂ (C1) and {6-[(2,6-Pr₂-C₆H₃)N=C(Me)]-2-C₆H₅N}FeCl₂ (C2) exhibited moderate trans-1,4 selectivity (>67%) while the iron-based systems bearing related aldiminopyridyl ligands {6-[(2,6-Me₂-C₆H₃)N=C(H)]-2-C₆H₅N}FeCl₂ (C3) and {6-[(2,6-Pr₂-C₆H₃)N=C(H)]-2-C₆H₅N}FeCl₂ (C4) were found to afford significant cis-1,4 selectivity at low temperature (>86% at -40 °C). On the other hand, the ternary {6-[(3,5-(CF₃)₂-C₆H₃)N=C(Me)]-2-C₆H₅N}FeCl₂ (C5) or {6-[(C₆F₅)N=C(Me)]-2-C₆H₅N}FeCl₂ (C6)/AlBu₃/[Ph₃C][B(C₆F₅)₄] catalytic combinations showed exceptional activity for the polymerization of isoprene (TOF > 1,000,000 h^-1), albeit providing less stereoselectivity.