“On/off” switchable ε‐caprolactone polymerization initiated by rare‐earth metal complexes supported by ferrocenyl‐functionalized arylamido ligands

Abstract

Redox‐switchable catalysis is an efficient process to modulate the activity and/or selectivity in the polymerization with greater polymerization control and precision. In this work, the ferrocenyl‐functionalized diarylamines 4‐Fc‐C6H4NHC6H5 (HL1), 4‐Fc‐C6H4NH(2,6‐Me2C6H3) (HL2), and 2,6‐iPr2–4‐Fc‐C6H2NHC6H5 (HL3) were prepared and used as pro‐ligands to obtain the arylamido‐ligated rare‐earth metal complexes. Treatment of RE (CH2C6H4NMe2‐o)3 with 1 equiv. of HL1–3 in toluene afforded the ferrocenyl‐functionalized‐arylamido rare‐earth metal bis(o‐dimethylaminobenzyl) complexes L1Sc(CH2C6H4NMe2‐o)2 (1), L2RE(CH2C6H4NMe2‐o)2 (RE = Sc (2), Y (3)), and L3Y(CH2C6H4NMe2‐o)2 (4) in good yields. The compositions of these complexes were verified by NMR spectroscopy and elemental analysis. HL1 and HL3 were subjected to single‐crystal X‐ray diffraction. Electrochemical and NMR studies indicated that 4 could be oxidized with AgBF4 to generate the corresponding oxidized species 4ox, which could be facilely reduced back to 4 by use of CoCp2 as the reductant. The redox‐reversible ability between 4 and 4ox gave the chance to modulate the reactivity by switching the oxidized and reduced forms of one complex. For a controlled polymerization of ε‐caprolactone, 4 was active, and the polymerization process could be easily “on/off” switched by the redox reaction occurred on the ferrocenyl moiety.