Journal
DALTON TRANSACTIONS
Volume 53, Issue 2, Pages 753-764Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d3dt03674j
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In this study, a series of structurally rigid cyclooctyl-fused iminopyridine iron complexes were synthesized and used with methylaluminoxane for isoprene polymerization. The extent of steric hindrance of the ligand framework was found to significantly affect catalytic performance, with less hindrance leading to better activity and stability.
In this study, a series of structurally rigid cyclooctyl-fused iminopyridine iron complexes, [L2FeCl][FeCl4] and [2L(3)Fe][Cl][3FeCl(4)], was synthesized via a one-pot method and investigated as precatalysts in conjunction with methylaluminoxane for isoprene (Ip) polymerization. Combined characterization through FTIR analysis, elemental analysis and single crystal XRD analysis fully verified the structure of these complexes. The most active iron complex, FeH, exhibited a trisligated nature, with its cation adopting an octahedral geometry around the metal center. In contrast, all the other iron complexes (Fe2Me, Fe2Et, Fe2iPr, Fe3Me, Fe2Et,Me) displayed bisligated configurations, with distorted trigonal bipyramidal geometry of cations. During isoprene polymerization, the extent of steric hindrance of the ligand framework exerted a significant impact on catalytic performance. The FeH precatalyst with less steric hindrance demonstrated excellent performance, producing high molecular weight polyisoprenes with conversions exceeding 99% for 4000 equiv. of monomer. Even at very low catalyst loadings, as low as 0.0025 mol% (Fe/Ip), the polymerization of isoprene could proceed smoothly with an exceptionally high activity of 4.0 x 10(6) g(PI) (mol(Fe), h)(-1). Moreover, this precatalyst exhibited good thermal stability, maintaining high activity levels (typically 10(5) g(PI) (mol(Fe), h)(-1)) across a broad temperature range from -20 degrees C to 100 degrees C. Additionally, by adjusting steric substituents and the reaction temperature, the 1,4/3,4 regioselectivity could be modulated from 9/91 to 69/31 while maintaining a high stereoselectivity of cis-1,4 structures (cis/trans: >99/1).
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