Lithium calix[4]arenes: structural studies and use in the ring opening polymerization of cyclic esters

We have structurally characterized a number of lithiated calix[4]arenes, where the bridge in the calix[4]arene is thia (–S–, L^SH₄), sulfinyl (–SO–, L^SOH₄), sulfonyl (–SO₂–, L^SO2H₄), dimethyleneoxa (–CH₂OCH₂–, L^COCH₄) or methylene (–CH₂–, LH₄). In the case of L^4SH₄, interaction with LiOtBu led to the isolation of the complex [Li₈(L^4S)₂(THF)₄]·5THF (1·5THF), whilst similar interaction of L^4SOH₄ led to the isolation of [Li₆(L^4SOH)₂(THF)₂]·5(THF) (2·5THF). Interestingly, the mixed sulfinyl/sulfonyl complexes [Li₈(calix[4]arene(SO)(SO₂)(SO_1.68)₂)₂(THF)₆]·8(THF) (3·8THF) and [Li₅Na(L^SO/3SO2H)₂(THF)₅]·7.5(THF) (4·7.5(THF) have also been characterized. Interaction of LiOtBu with L^SO2H₄ and L^COCH₄ afforded [Li₅L^4SO2(OH)(THF)₄]·2THF (5·2THF) and [Li₆(L^COC)₂(HOtBu)₂]·0.78THF·1.22hexane (6·0.78THF·1.22hexane), respectively. In the case of LH₄, reaction with LiOtBu in THF afforded a monoclinic polymorph [LH₂Li₂(thf)(OH₂)₂]·3THF (7·3THF) of a known triclinic form of the complex, whilst reaction of the de-butylated analogue of LH₄, namely de-BuLH₄, afforded a polymeric chain structure {[Li₅(de-BuL)(OH)(NCMe)₃]·2MeCN}_n (8·2MeCN). For comparative catalytic studies, the complex [Li₆(L^Pr)₂(H₂O)₂]·hexane (9 hexane), where L^Pr2H₂ = 1,3-di-n-propyloxycalix[4]areneH₂, was also prepared. The molecular crystal structures of 1–9 are reported, and their ability to act as catalysts for the ring opening (co-)/polymerization (ROP) of the cyclic esters ε-caprolactone, δ-valerolactone, and rac-lactide has been investigated. In most of the cases, complex 6 outperformed the other systems, allowing for higher conversions and/or greated polymer M_n.