Abstract
Anilido-oxazoline-ligated iron complexes, including bis(anilido-oxazolinate) iron(II), mononuclear iron(II) alkyl and aryloxide, as well as the dinuclear analogues, were synthesized, and their catalytic performance on ring-opening polymerization (ROP) has been studied. Transmetalation of FeCl2(THF)1.5 with in situ-generated anilido-oxazolinate lithium afforded the bis(anilido-oxazolinate) iron complexes 1 and 2. Half-sandwich anilido-oxazolinate iron trimethylsilylalkyl complexes 3 and 4 could be synthesized in good yields via taking pyridine as an L-type ligand. Treatment of 3 with benzyl alcohol and 4-phenoxyphenol, respectively, generated the dimeric alkoxide or aryloxide complexes 5 and 6, whereas the reaction with 2,4,6-trimethylphenol and 2,6-di-tert-butyl-4-methylphenol yielded the mononuclear aryloxide complexes 7 and 8, respectively. The iron alkoxide and aryloxide complexes were active single component catalysts for the ROP of ε-caprolactone (CL). Remarkably, the dinuclear complex 5 exhibited excellent controllability, livingness, and high initiation efficiency for ROP of CL. ROP of CL derivatives by 5 produced the corresponding polycyclic esters with good controllability, and the well-defined block copolymers could be generated by sequentially feeding different monomers. The chain initiation and propagation processes were investigated by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and kinetics analysis. In addition, a computational study was conducted to rationalize the mechanism and synergistic effect of the alkoxide-bridged bimetallic iron centers.
Published Version
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